CN103724938A - Method for preparing nano-copper/epoxy resin composite material - Google Patents
Method for preparing nano-copper/epoxy resin composite material Download PDFInfo
- Publication number
- CN103724938A CN103724938A CN201310653506.8A CN201310653506A CN103724938A CN 103724938 A CN103724938 A CN 103724938A CN 201310653506 A CN201310653506 A CN 201310653506A CN 103724938 A CN103724938 A CN 103724938A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- copper
- composite material
- nanometer copper
- cuso
- 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.)
- Granted
Links
Images
Abstract
The invention provides a method for preparing a nano-copper/epoxy resin composite material, relates to a preparation method of an epoxy resin composite material, and aims to solve the problem that nano-copper powder in an existing nano-copper/epoxy resin composite material is easy to cluster, and the dispersibility in the epoxy resin is poor, so that a mechanical property of the nano-copper/epoxy resin composite material is poor. The method comprises the following steps: 1, preparing nano-copper powder; 2, dispersing; 3, preparing a composite material. The nano-copper/epoxy resin composite material prepared by the method has the advantages that: 1, the copper powder in the nano-copper/epoxy resin composite material is nanoscale; 2, the oxidation of the nano-copper powder is effectively prevented; 3, an emulsifying machine is used to disperse a nano-copper/epoxy resin system, the method is simple, and the dispersibility is good; 4, the nano-copper/epoxy resin composite material prepared by the invention has the characteristics that the tensile strength is 38-50 MPa, the elastic modulus is 1200-1700 MPa and the hardness is 80-84 degrees. The method can be used to prepare the nano-copper/epoxy resin composite material.
Description
Technical field
The present invention relates to a kind of preparation method of epoxy resin composite material.
Background technology
Epoxy resin is as the Typical Representative of thermosetting resin, there are a lot of outstanding performances, as excellent mechanical property, electrical insulation capability is good, and shrinking percentage is low, adhesiveproperties is good, chemical resistant properties, good processing characteristics, cheap etc., these make its application very extensive, are widely used in the fields such as coating, sizing agent, electronic instrument, aerospace.But the cross-linking density after epoxy resin cure is large, is tridimensional network, exist that matter is crisp, poor impact resistance, resistance to fatigue and the shortcoming such as thermotolerance is poor, internal stress is large, this has limited its application to a great extent.And epoxy/nanocomposites be now in type material tool great-hearted, it can effectively combine performance excellent some of nanoparticle and epoxy resin, as thermostability, rigidity etc.And the activity of nanoparticle is high, easily there is physics chemical action with the functional group of epoxy resin, and then improve calorifics, optics, mechanics and the electromagnetic property etc. of epoxy resin cured product.
Copper nanoparticle is little owing to having size, and the features such as specific surface area large and quantum size effect and macro quanta tunnel effect, therefore have the property that is different from block and macrobead copper material.And the scattering problem of copper nanoparticle in epoxy resin is very scabrous, because copper nanoparticle is easily reunited, easily cause matrix material stress concentration, in matrix material, form defect, affect the mechanical property of matrix material.And for solving the scattering problem of copper nanoparticle in epoxy resin, be mainly to have several method at present: surface chemical modification, dispersion agent disperses, ultrasonic dispersion, mechanical dispersion and solvent dispersion.General some auxiliary agents of interpolation that adopt are realized the scattering problem of copper nanoparticle in epoxy resin at present, at present Nanometer Copper/epoxy resin composite material exists copper nanoparticle easily to reunite, bad dispersibility in epoxy resin and the low problem of Nanometer Copper/epoxy resin composite material mechanical property that causes.
Summary of the invention
The object of the invention is to solve existing Nanometer Copper/epoxy resin composite material exists copper nanoparticle easily to reunite, bad dispersibility in epoxy resin and the low problem of Nanometer Copper/epoxy resin composite material mechanical property that causes, and a kind of preparation method of Nanometer Copper/epoxy resin composite material is provided.
A kind of preparation method of Nanometer Copper/epoxy resin composite material specifically completes according to the following steps:
One, prepare copper nanoparticle: 1. under room temperature take distilled water as solvent, utilize ultrasonic method by CuSO
45H
2o dissolves completely, obtains CuSO
4the aqueous solution; 2. the CuSO 1. obtaining to step 1
4in the aqueous solution, add PVP, ultrasonic 30min～50min, obtains PVP/CuSO
4mixed aqueous solution; 3. under room temperature, hydrazine hydrate is mixed with distilled water, obtain hydrazine hydrate solution; 4. under room temperature take distilled water as solvent, after NaOH is dissolved completely, obtain NaOH solution; 5. PVP/the CuSO first 2. step 1 being obtained
4mixed aqueous solution joins in three neck round-bottomed flasks, then to the hydrazine hydrate solution that adds step 1 3. to obtain in three neck round-bottomed flasks, the NaOH solution that adds step 1 4. to obtain in the most backward three neck round-bottomed flasks, in temperature, be to stir 20min～25min under 65 ℃～75 ℃ and the rotating speed condition that is 250r/min～350r/min, then use distilled water filtering and washing 2h～3h, in vacuum tightness, be vacuum-drying 2h～4h under 0.08MPa～0.09MPa and room temperature condition again, obtain copper nanoparticle;
The CuSO of step 1 described in 1.
45H
2the quality of O and the volume ratio of distilled water are (0.125g～0.25g): 1mL;
Quality and the CuSO of the PVP of step 1 described in 2.
4the volume ratio of the aqueous solution is (0.0125g～0.025g): 1mL;
The volume of hydrazine hydrate and the volume ratio of distilled water of step 1 described in is 3. (3～5): 1;
The quality of the NaOH of step 1 described in 4. with the volume ratio of distilled water be (0.2g～0.35g): 1mL;
PVP/the CuSO of step 1 described in 5.
4the volume of mixed aqueous solution and the volume ratio of hydrazine hydrate solution are (0.8～1.25): 1;
PVP/the CuSO of step 1 described in 5.
4the volume ratio of the volume of mixed aqueous solution and NaOH solution is (2～3): 1;
Two, disperse: the copper nanoparticle that 5. step 1 is obtained joins in epoxy resin, use mulser under the rotating speed of rotating speed 7000r/min～8000r/min, to carry out emulsion dispersion 5min～7min, obtain Nanometer Copper/epoxy resin composition;
The quality of the copper nanoparticle described in step 2 and the mass ratio of epoxy resin are (0.005～0.35): 1;
Three, prepare matrix material: the Nanometer Copper/epoxy resin composition 1. step 2 being obtained and solidifying agent be preheating 1.5h～2h under the condition of 55 ℃～65 ℃ respectively, obtains the solidifying agent after Nanometer Copper/epoxy resin composition and the preheating after preheating; 2. the solidifying agent after Nanometer Copper/epoxy resin composition and preheating after the preheating 1. step 3 being obtained is to stir 4min～5min under 90r/min～110r/min at rotating speed, obtains Nanometer Copper/epoxy prepolymer; 3. will scribble tetrafluoroethylene mould preheating 1.5h～2h at the temperature of 55 ℃～65 ℃ of high vacuum silicone grease, obtain the tetrafluoroethylene mould that scribbles high vacuum silicone grease of preheating; 4. Nanometer Copper/the epoxy prepolymer first 2. step 3 being obtained is poured step 3 into 3. in the tetrafluoroethylene mould that scribbles high vacuum silicone grease of preheating, then the tetrafluoroethylene mould that scribbles high vacuum silicone grease is put into baking oven and at 65 ℃～75 ℃ of temperature, solidified successively 2h～2.5h, in temperature, be at 120 ℃～130 ℃, to solidify 2h～3h, in temperature, be at 145 ℃～155 ℃, to solidify 1h～1.5h, obtain Nanometer Copper/epoxy resin composite material;
Step 3 1. described solidifying agent is Versamid;
The step 3 1. mass ratio of the epoxy resin described in quality and the step 2 of described solidifying agent is (0.4～0.5): 1.
Advantage of the present invention: in Nanometer Copper/epoxy resin composite material that, prepared by the present invention copper powder size at nano level, dimensional stabilizing; Two, the present invention, take hydrazine hydrate as reductive agent, produces nitrogen in reaction process, has effectively prevented the oxidation of copper nanoparticle; Three, adopt mulser to disperse Nanometer Copper/epoxy-resin systems, method is simple, good dispersity, do not need to add any coating materials and coupling agent, carry out emulsion dispersion with mulser, dispersion effect is good, and Nanometer Copper/epoxy resin composite material mechanical property improves; Tensile strength 38MPa～the 50MPa of Nanometer Copper/epoxy resin composite material that four, prepared by the present invention, Young's modulus 1200MPa～1700MPa, 80 °～84 ° of hardness.
The present invention can prepare Nanometer Copper/epoxy resin composite material.
Accompanying drawing explanation
Fig. 1 is that the Nanometer Copper/epoxy resin composite material of test one preparation amplifies the SEM figure of 1000 times;
Fig. 2 is that the Nanometer Copper/epoxy resin composite material of test two preparations amplifies the SEM figure of 1000 times;
Fig. 3 is that the Nanometer Copper/epoxy resin composite material of test three preparations amplifies the SEM figure of 1000 times;
Fig. 4 is that the Nanometer Copper/epoxy resin composite material of test four preparations amplifies the SEM figure of 1000 times.
Embodiment
Embodiment one: present embodiment is that a kind of preparation method of Nanometer Copper/epoxy resin composite material specifically completes according to the following steps:
One, prepare copper nanoparticle: 1. under room temperature take distilled water as solvent, utilize ultrasonic method by CuSO
45H
2o dissolves completely, obtains CuSO
4the aqueous solution; 2. the CuSO 1. obtaining to step 1
4in the aqueous solution, add PVP, ultrasonic 30min～50min, obtains PVP/CuSO
4mixed aqueous solution; 3. under room temperature, hydrazine hydrate is mixed with distilled water, obtain hydrazine hydrate solution; 4. under room temperature take distilled water as solvent, after NaOH is dissolved completely, obtain NaOH solution; 5. PVP/the CuSO first 2. step 1 being obtained
4mixed aqueous solution joins in three neck round-bottomed flasks, then to the hydrazine hydrate solution that adds step 1 3. to obtain in three neck round-bottomed flasks, the NaOH solution that adds step 1 4. to obtain in the most backward three neck round-bottomed flasks, in temperature, be to stir 20min～25min under 65 ℃～75 ℃ and the rotating speed condition that is 250r/min～350r/min, then use distilled water filtering and washing 2h～3h, in vacuum tightness, be vacuum-drying 2h～4h under 0.08MPa～0.09MPa and room temperature condition again, obtain copper nanoparticle;
The CuSO of step 1 described in 1.
45H
2the quality of O and the volume ratio of distilled water are (0.125g～0.25g): 1mL;
Quality and the CuSO of the PVP of step 1 described in 2.
4the volume ratio of the aqueous solution is (0.0125g～0.025g): 1mL;
The volume of hydrazine hydrate and the volume ratio of distilled water of step 1 described in is 3. (3～5): 1;
The quality of the NaOH of step 1 described in 4. with the volume ratio of distilled water be (0.2g～0.35g): 1mL;
PVP/the CuSO of step 1 described in 5.
4the volume of mixed aqueous solution and the volume ratio of hydrazine hydrate solution are (0.8～1.25): 1;
PVP/the CuSO of step 1 described in 5.
4the volume ratio of the volume of mixed aqueous solution and NaOH solution is (2～3): 1;
Two, disperse: the copper nanoparticle that 5. step 1 is obtained joins in epoxy resin, use mulser under the rotating speed of rotating speed 7000r/min～8000r/min, to carry out emulsion dispersion 5min～7min, obtain Nanometer Copper/epoxy resin composition;
The quality of the copper nanoparticle described in step 2 and the mass ratio of epoxy resin are (0.005～0.35): 1;
Three, prepare matrix material: the Nanometer Copper/epoxy resin composition 1. step 2 being obtained and solidifying agent be preheating 1.5h～2h under the condition of 55 ℃～65 ℃ respectively, obtains the solidifying agent after Nanometer Copper/epoxy resin composition and the preheating after preheating; 2. the solidifying agent after Nanometer Copper/epoxy resin composition and preheating after the preheating 1. step 3 being obtained is to stir 4min～5min under 90r/min～110r/min at rotating speed, obtains Nanometer Copper/epoxy prepolymer; 3. will scribble tetrafluoroethylene mould preheating 1.5h～2h at the temperature of 55 ℃～65 ℃ of high vacuum silicone grease, obtain the tetrafluoroethylene mould that scribbles high vacuum silicone grease of preheating; 4. Nanometer Copper/the epoxy prepolymer first 2. step 3 being obtained is poured step 3 into 3. in the tetrafluoroethylene mould that scribbles high vacuum silicone grease of preheating, then the tetrafluoroethylene mould that scribbles high vacuum silicone grease is put into baking oven and at 65 ℃～75 ℃ of temperature, solidified successively 2h～2.5h, in temperature, be at 120 ℃～130 ℃, to solidify 2h～3h, in temperature, be at 145 ℃～155 ℃, to solidify 1h～1.5h, obtain Nanometer Copper/epoxy resin composite material;
Step 3 1. described solidifying agent is Versamid;
The step 3 1. mass ratio of the epoxy resin described in quality and the step 2 of described solidifying agent is (0.4～0.5): 1.
Present embodiment can be prepared Nanometer Copper/epoxy resin composite material.
Nanometer Copper/epoxy resin composition and solidifying agent preheating 1.5h～2h under the condition of 55 ℃～65 ℃ that present embodiment step 3 obtains step 2 in 1.; Nanometer Copper/epoxy resin composition after the preheating that 1. step 3 obtains step 3 in 2. and solidifying agent are that the object that stirs 4min～5min under 90r/min～110r/min is to discharge be rolled in the bubble in epoxy resin and solidifying agent is uniformly dispersed in Nanometer Copper/epoxy resin composition at rotating speed.
Present embodiment, take hydrazine hydrate as reductive agent, produces nitrogen in reaction process, effectively prevented the oxidation of copper nanoparticle.
The advantage of present embodiment: in Nanometer Copper/epoxy resin composite material that, prepared by present embodiment copper powder size at nano level, dimensional stabilizing; Two, present embodiment, take hydrazine hydrate as reductive agent, produces nitrogen in reaction process, has effectively prevented the oxidation of copper nanoparticle; Three, adopt mulser to disperse Nanometer Copper/epoxy-resin systems, method is simple, good dispersity, do not need to add any coating materials and coupling agent, carry out emulsion dispersion with mulser, dispersion effect is good, and Nanometer Copper/epoxy resin composite material mechanical property improves; Tensile strength 38MPa～the 50MPa of Nanometer Copper/epoxy resin composite material that four, prepared by present embodiment, Young's modulus 1200MPa～1700MPa, 80 °～84 ° of hardness.
Embodiment two: present embodiment and embodiment one difference are: the CuSO of step 1 described in 1.
45H
2the quality of O and the volume ratio of distilled water are (0.15g～0.2g): 1mL.Other steps are identical with embodiment one.
Embodiment three: one of present embodiment and embodiment one or two difference is: quality and the CuSO of the PVP of step 1 described in 2.
4the volume ratio of the aqueous solution is (0.015g～0.025g): 1mL.Other steps are identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three difference is: the quality of the NaOH of step 1 described in 4. with the volume ratio of distilled water be (0.25g～0.35g): 1mL.Other steps are identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four difference is: the PVP/CuSO of step 1 described in 5.
4the volume of mixed aqueous solution and the volume ratio of hydrazine hydrate solution are (0.9～1.25): 1.Other steps are identical with embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five difference is: the PVP/CuSO of step 1 described in 5.
4the volume ratio of the volume of mixed aqueous solution and NaOH solution is (2.5～3): 1.Other steps are identical with embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six difference is: the quality of the copper nanoparticle described in step 2 and the mass ratio of epoxy resin are (0.001～0.28): 1.Other steps are identical with embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven difference is: Nanometer Copper/epoxy resin composition and the solidifying agent after preheating after the preheating that 1. step step 3 obtains step 3 in are 2. to stir 4.5min～5min under 95r/min～110r/min at rotating speed, obtain Nanometer Copper/epoxy prepolymer.Other steps are identical with embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight difference is: Nanometer Copper/epoxy prepolymer that 2. first step 3 obtain step 3 in is 4. poured step 3 into 3. in the tetrafluoroethylene mould that scribbles high vacuum silicone grease of preheating, then the tetrafluoroethylene mould that scribbles high vacuum silicone grease is put into baking oven and at 68 ℃～75 ℃ of temperature, solidified successively 2h～2.5h, in temperature, be at 125 ℃～130 ℃, to solidify 2.5h～3h, in temperature, be at 150 ℃～155 ℃, to solidify 1h～1.5h, obtain Nanometer Copper/epoxy resin composite material.Other steps are identical with embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine difference is: the step 3 1. mass ratio of the epoxy resin described in quality and the step 2 of described solidifying agent is (0.45～0.5): 1.Other steps are identical with embodiment one to nine.
Adopt following verification experimental verification beneficial effect of the present invention:
Test one: a kind of preparation method of Nanometer Copper/epoxy resin composite material specifically completes according to the following steps:
One, prepare copper nanoparticle: 1. under room temperature take distilled water as solvent, utilize ultrasonic method by CuSO
45H
2o dissolves completely, obtains CuSO
4the aqueous solution; 2. the CuSO 1. obtaining to step 1
4in the aqueous solution, add PVP, ultrasonic 50min, obtains PVP/CuSO
4mixed aqueous solution; 3. under room temperature, hydrazine hydrate is mixed with distilled water, obtain hydrazine hydrate solution; 4. under room temperature take distilled water as solvent, after NaOH is dissolved completely, obtain NaOH solution; 5. PVP/the CuSO first 2. step 1 being obtained
4mixed aqueous solution joins in three neck round-bottomed flasks, then to the hydrazine hydrate solution that adds step 1 3. to obtain in three neck round-bottomed flasks, the NaOH solution that adds step 1 4. to obtain in the most backward three neck round-bottomed flasks, in temperature, be to stir 20min under 70 ℃ and the rotating speed condition that is 300r/min, then use distilled water filtering and washing 3h, in vacuum tightness, be vacuum-drying 4h under 0.09MPa and room temperature condition again, obtain copper nanoparticle;
The CuSO of step 1 described in 1.
45H
2the quality of O and the volume ratio of distilled water are 0.125g:1mL;
Quality and the CuSO of the PVP of step 1 described in 2.
4the volume ratio of the aqueous solution is 0.0125g:1mL;
The volume of hydrazine hydrate and the volume ratio of distilled water of step 1 described in is 3. 3:1;
The quality of the NaOH of step 1 described in 4. with the volume ratio of distilled water be 0.21g:1mL;
PVP/the CuSO of step 1 described in 5.
4the volume of mixed aqueous solution and the volume ratio of hydrazine hydrate solution are 1.25:1;
PVP/the CuSO of step 1 described in 5.
4the volume ratio of the volume of mixed aqueous solution and NaOH solution is 2.5:1;
Two, disperse: the copper nanoparticle that 5. step 1 is obtained joins in epoxy resin, use mulser under the rotating speed of rotating speed 7500r/min, to carry out emulsion dispersion 5min～7min, obtain Nanometer Copper/epoxy resin composition;
The quality of the copper nanoparticle described in step 2 and the mass ratio of epoxy resin are 0.01:1;
Three, prepare matrix material: the Nanometer Copper/epoxy resin composition 1. step 2 being obtained and solidifying agent be preheating 2h under the condition of 60 ℃ respectively, obtain the solidifying agent after Nanometer Copper/epoxy resin composition and the preheating after preheating; 2. the solidifying agent after Nanometer Copper/epoxy resin composition and preheating after the preheating 1. step 3 being obtained is to stir 4min～5min under 100r/min at rotating speed, obtains Nanometer Copper/epoxy prepolymer; 3. will scribble tetrafluoroethylene mould preheating 2h at the temperature of 60 ℃ of high vacuum silicone grease, obtain the tetrafluoroethylene mould that scribbles high vacuum silicone grease of preheating; 4. Nanometer Copper/the epoxy prepolymer first 2. step 3 being obtained is poured step 3 into 3. in the tetrafluoroethylene mould that scribbles high vacuum silicone grease of preheating, then the tetrafluoroethylene mould that scribbles high vacuum silicone grease is put into baking oven and under temperature 70 C, solidified successively 2h, in temperature, be at 125 ℃, to solidify 2.5h, in temperature, be at 150 ℃, to solidify 1h, obtain Nanometer Copper/epoxy resin composite material;
Step 3 1. described solidifying agent is Versamid;
The step 3 1. mass ratio of the epoxy resin described in quality and the step 2 of described solidifying agent is 0.5:1.
Use scanning electron microscope to analyze Nanometer Copper/epoxy resin composite material of testing a preparation, as shown in Figure 1, Fig. 1 is that the Nanometer Copper/epoxy resin composite material of test one preparation amplifies the SEM figure of 1000 times, the dispersiveness of copper nanoparticle in epoxy resin is better as can be seen from Figure 1, do not reunite, add after appropriate copper nanoparticle, the section of matrix material becomes coarse injustice, between visible copper nanoparticle and epoxy resin, there is certain interfacial interaction, can effectively prevent the concentrated destruction causing of matrix material stress, thereby improve the mechanical property of epoxy resin.
Use microcomputer control universal testing machine to test the mechanical property of Nanometer Copper/epoxy resin composite material of testing a preparation, the tensile strength of Nanometer Copper/epoxy resin composite material prepared by known test one is 38.973MPa, Young's modulus is 1297.234MPa, hardness is 82.45 °, with pure epoxy resin tensile strength 34.146MPa, Young's modulus 804.167MPa, hardness is 82.07 ° and compares and improved respectively 14%, 61% and 0.5%.
Test two: a kind of preparation method of Nanometer Copper/epoxy resin composite material specifically completes according to the following steps:
One, prepare copper nanoparticle: 1. under room temperature take distilled water as solvent, utilize ultrasonic method by CuSO
45H
2o dissolves completely, obtains CuSO
4the aqueous solution; 2. the CuSO 1. obtaining to step 1
4in the aqueous solution, add PVP, ultrasonic 50min, obtains PVP/CuSO
4mixed aqueous solution; 3. under room temperature, hydrazine hydrate is mixed with distilled water, obtain hydrazine hydrate solution; 4. under room temperature take distilled water as solvent, after NaOH is dissolved completely, obtain NaOH solution; 5. PVP/the CuSO first 2. step 1 being obtained
4mixed aqueous solution joins in three neck round-bottomed flasks, then to the hydrazine hydrate solution that adds step 1 3. to obtain in three neck round-bottomed flasks, the NaOH solution that adds step 1 4. to obtain in the most backward three neck round-bottomed flasks, in temperature, be to stir 20min under 70 ℃ and the rotating speed condition that is 300r/min, then use distilled water filtering and washing 3h, in vacuum tightness, be vacuum-drying 4h under 0.09MPa and room temperature condition again, obtain copper nanoparticle;
The CuSO of step 1 described in 1.
45H
2the quality of O and the volume ratio of distilled water are 0.125g:1mL;
Quality and the CuSO of the PVP of step 1 described in 2.
4the volume ratio of the aqueous solution is 0.0125g:1mL;
The volume of hydrazine hydrate and the volume ratio of distilled water of step 1 described in is 3. 3:1;
The quality of the NaOH of step 1 described in 4. with the volume ratio of distilled water be 0.21g:1mL;
PVP/the CuSO of step 1 described in 5.
4the volume of mixed aqueous solution and the volume ratio of hydrazine hydrate solution are 1.25:1;
PVP/the CuSO of step 1 described in 5.
4the volume ratio of the volume of mixed aqueous solution and NaOH solution is 2.5:1;
Two, disperse: the copper nanoparticle that 5. step 1 is obtained joins in epoxy resin, use mulser under the rotating speed of rotating speed 7500r/min, to carry out emulsion dispersion 5min～7min, obtain Nanometer Copper/epoxy resin composition;
The quality of the copper nanoparticle described in step 2 and the mass ratio of epoxy resin are 0.02:1;
Three, prepare matrix material: the Nanometer Copper/epoxy resin composition 1. step 2 being obtained and solidifying agent be preheating 2h under the condition of 60 ℃ respectively, obtain the solidifying agent after Nanometer Copper/epoxy resin composition and the preheating after preheating; 2. the solidifying agent after Nanometer Copper/epoxy resin composition and preheating after the preheating 1. step 3 being obtained is to stir 4min～5min under 100r/min at rotating speed, obtains Nanometer Copper/epoxy prepolymer; 3. will scribble tetrafluoroethylene mould preheating 2h at the temperature of 60 ℃ of high vacuum silicone grease, obtain the tetrafluoroethylene mould that scribbles high vacuum silicone grease of preheating; 4. Nanometer Copper/the epoxy prepolymer first 2. step 3 being obtained is poured step 3 into 3. in the tetrafluoroethylene mould that scribbles high vacuum silicone grease of preheating, then the tetrafluoroethylene mould that scribbles high vacuum silicone grease is put into baking oven and under temperature 70 C, solidified successively 2h, in temperature, be at 125 ℃, to solidify 2.5h, in temperature, be at 150 ℃, to solidify 1h, obtain Nanometer Copper/epoxy resin composite material;
Step 3 1. described solidifying agent is Versamid;
The step 3 1. mass ratio of the epoxy resin described in quality and the step 2 of described solidifying agent is 0.5:1.
Use scanning electron microscope to analyze Nanometer Copper/epoxy resin composite material of testing two preparations, as shown in Figure 2, Fig. 2 is that the Nanometer Copper/epoxy resin composite material of test two preparations amplifies the SEM figure of 1000 times, the dispersiveness of copper nanoparticle in epoxy resin is better as can be seen from Figure 2, do not reunite, add after appropriate copper nanoparticle, the section of matrix material becomes coarse injustice, between visible copper nanoparticle and epoxy resin, there is certain interfacial interaction, can effectively prevent the concentrated destruction causing of matrix material stress, thereby improve the mechanical property of epoxy resin.
Use microcomputer control universal testing machine to test the mechanical property of Nanometer Copper/epoxy resin composite material of testing two preparations, the tensile strength of Nanometer Copper/epoxy resin composite material prepared by known test two is 41.239MPa, Young's modulus is 1421.257MPa, hardness is 82.72 °, with pure epoxy resin tensile strength 34.146MPa, Young's modulus 804.167MPa, hardness is 82.07 ° and compares and improved respectively 21%, 77% and 0.8%.
Test three: a kind of preparation method of Nanometer Copper/epoxy resin composite material specifically completes according to the following steps:
One, prepare copper nanoparticle: 1. under room temperature take distilled water as solvent, utilize ultrasonic method by CuSO
45H
2o dissolves completely, obtains CuSO
4the aqueous solution; 2. the CuSO 1. obtaining to step 1
4in the aqueous solution, add PVP, ultrasonic 50min, obtains PVP/CuSO
4mixed aqueous solution; 3. under room temperature, hydrazine hydrate is mixed with distilled water, obtain hydrazine hydrate solution; 4. under room temperature take distilled water as solvent, after NaOH is dissolved completely, obtain NaOH solution; 5. PVP/the CuSO first 2. step 1 being obtained
4mixed aqueous solution joins in three neck round-bottomed flasks, then to the hydrazine hydrate solution that adds step 1 3. to obtain in three neck round-bottomed flasks, the NaOH solution that adds step 1 4. to obtain in the most backward three neck round-bottomed flasks, in temperature, be to stir 20min under 70 ℃ and the rotating speed condition that is 300r/min, then use distilled water filtering and washing 3h, in vacuum tightness, be vacuum-drying 4h under 0.09MPa and room temperature condition again, obtain copper nanoparticle;
The CuSO of step 1 described in 1.
45H
2the quality of O and the volume ratio of distilled water are 0.125g:1mL;
Quality and the CuSO of the PVP of step 1 described in 2.
4the volume ratio of the aqueous solution is 0.0125g:1mL;
The volume of hydrazine hydrate and the volume ratio of distilled water of step 1 described in is 3. 3:1;
The quality of the NaOH of step 1 described in 4. with the volume ratio of distilled water be 0.21g:1mL;
PVP/the CuSO of step 1 described in 5.
4the volume of mixed aqueous solution and the volume ratio of hydrazine hydrate solution are 1.25:1;
PVP/the CuSO of step 1 described in 5.
4the volume ratio of the volume of mixed aqueous solution and NaOH solution is 2.5:1;
Two, disperse: the copper nanoparticle that 5. step 1 is obtained joins in epoxy resin, use mulser under the rotating speed of rotating speed 7500r/min, to carry out emulsion dispersion 5min～7min, obtain Nanometer Copper/epoxy resin composition;
The quality of the copper nanoparticle described in step 2 and the mass ratio of epoxy resin are 0.04:1;
Three, prepare matrix material: the Nanometer Copper/epoxy resin composition 1. step 2 being obtained and solidifying agent be preheating 2h under the condition of 60 ℃ respectively, obtain the solidifying agent after Nanometer Copper/epoxy resin composition and the preheating after preheating; 2. the solidifying agent after Nanometer Copper/epoxy resin composition and preheating after the preheating 1. step 3 being obtained is to stir 4min～5min under 100r/min at rotating speed, obtains Nanometer Copper/epoxy prepolymer; 3. will scribble tetrafluoroethylene mould preheating 2h at the temperature of 60 ℃ of high vacuum silicone grease, obtain the tetrafluoroethylene mould that scribbles high vacuum silicone grease of preheating; 4. Nanometer Copper/the epoxy prepolymer first 2. step 3 being obtained is poured step 3 into 3. in the tetrafluoroethylene mould that scribbles high vacuum silicone grease of preheating, then the tetrafluoroethylene mould that scribbles high vacuum silicone grease is put into baking oven and under temperature 70 C, solidified successively 2h, in temperature, be at 125 ℃, to solidify 2.5h, in temperature, be at 150 ℃, to solidify 1h, obtain Nanometer Copper/epoxy resin composite material;
Step 3 1. described solidifying agent is Versamid;
The step 3 1. mass ratio of the epoxy resin described in quality and the step 2 of described solidifying agent is 0.5:1.
Use scanning electron microscope to analyze Nanometer Copper/epoxy resin composite material of testing three preparations, as shown in Figure 3, Fig. 3 is that the Nanometer Copper/epoxy resin composite material of test three preparations amplifies the SEM figure of 1000 times, the dispersiveness of copper nanoparticle in epoxy resin is better as can be seen from Figure 3, do not reunite, add after appropriate copper nanoparticle, the section of matrix material becomes coarse injustice, between visible copper nanoparticle and epoxy resin, there is certain interfacial interaction, can effectively prevent the concentrated destruction causing of matrix material stress, thereby improve the mechanical property of epoxy resin.
Use microcomputer control universal testing machine to test the mechanical property of Nanometer Copper/epoxy resin composite material of testing three preparations, the tensile strength of Nanometer Copper/epoxy resin composite material prepared by known test three is 44.908MPa, Young's modulus is 1562.258MPa, hardness is 83.15 °, with pure epoxy resin tensile strength 34.146MPa, Young's modulus 804.167MPa, hardness is 82.07 ° and compares and improved respectively 32%, 94% and 1.3%.
Test four: a kind of preparation method of Nanometer Copper/epoxy resin composite material specifically completes according to the following steps:
One, prepare copper nanoparticle: 1. under room temperature take distilled water as solvent, utilize ultrasonic method by CuSO
45H
2o dissolves completely, obtains CuSO
4the aqueous solution; 2. the CuSO 1. obtaining to step 1
4in the aqueous solution, add PVP, ultrasonic 50min, obtains PVP/CuSO
4mixed aqueous solution; 3. under room temperature, hydrazine hydrate is mixed with distilled water, obtain hydrazine hydrate solution; 4. under room temperature take distilled water as solvent, after NaOH is dissolved completely, obtain NaOH solution; 5. PVP/the CuSO first 2. step 1 being obtained
4mixed aqueous solution joins in three neck round-bottomed flasks, then to the hydrazine hydrate solution that adds step 1 3. to obtain in three neck round-bottomed flasks, the NaOH solution that adds step 1 4. to obtain in the most backward three neck round-bottomed flasks, in temperature, be to stir 20min under 70 ℃ and the rotating speed condition that is 300r/min, then use distilled water filtering and washing 3h, in vacuum tightness, be vacuum-drying 4h under 0.09MPa and room temperature condition again, obtain copper nanoparticle;
The CuSO of step 1 described in 1.
45H
2the quality of O and the volume ratio of distilled water are 0.125g:1mL;
Quality and the CuSO of the PVP of step 1 described in 2.
4the volume ratio of the aqueous solution is 0.0125g:1mL;
The volume of hydrazine hydrate and the volume ratio of distilled water of step 1 described in is 3. 3:1;
The quality of the NaOH of step 1 described in 4. with the volume ratio of distilled water be 0.21g:1mL;
PVP/the CuSO of step 1 described in 5.
4the volume of mixed aqueous solution and the volume ratio of hydrazine hydrate solution are 1.25:1;
PVP/the CuSO of step 1 described in 5.
4the volume ratio of the volume of mixed aqueous solution and NaOH solution is 2.5:1;
Two, disperse: the copper nanoparticle that 5. step 1 is obtained joins in epoxy resin, use mulser under the rotating speed of rotating speed 7500r/min, to carry out emulsion dispersion 5min～7min, obtain Nanometer Copper/epoxy resin composition;
The quality of the copper nanoparticle described in step 2 and the mass ratio of epoxy resin are 0.08:1;
Three, prepare matrix material: the Nanometer Copper/epoxy resin composition 1. step 2 being obtained and solidifying agent be preheating 2h under the condition of 60 ℃ respectively, obtain the solidifying agent after Nanometer Copper/epoxy resin composition and the preheating after preheating; 2. the solidifying agent after Nanometer Copper/epoxy resin composition and preheating after the preheating 1. step 3 being obtained is to stir 4min～5min under 100r/min at rotating speed, obtains Nanometer Copper/epoxy prepolymer; 3. will scribble tetrafluoroethylene mould preheating 2h at the temperature of 60 ℃ of high vacuum silicone grease, obtain the tetrafluoroethylene mould that scribbles high vacuum silicone grease of preheating; 4. Nanometer Copper/the epoxy prepolymer first 2. step 3 being obtained is poured step 3 into 3. in the tetrafluoroethylene mould that scribbles high vacuum silicone grease of preheating, then the tetrafluoroethylene mould that scribbles high vacuum silicone grease is put into baking oven and under temperature 70 C, solidified successively 2h, in temperature, be at 125 ℃, to solidify 2.5h, in temperature, be at 150 ℃, to solidify 1h, obtain Nanometer Copper/epoxy resin composite material;
Step 3 1. described solidifying agent is Versamid;
The step 3 1. mass ratio of the epoxy resin described in quality and the step 2 of described solidifying agent is 0.5:1.
Use scanning electron microscope to analyze Nanometer Copper/epoxy resin composite material of testing four preparations, as shown in Figure 4, Fig. 4 is that the Nanometer Copper/epoxy resin composite material of test four preparations amplifies the SEM figure of 1000 times, the dispersiveness of copper nanoparticle in epoxy resin is better as can be seen from Figure 4, do not reunite, add after appropriate copper nanoparticle, the section of matrix material becomes coarse injustice, between visible copper nanoparticle and epoxy resin, there is certain interfacial interaction, can effectively prevent the concentrated destruction causing of matrix material stress, thereby improve the mechanical property of epoxy resin.
Use microcomputer control universal testing machine to test the mechanical property of Nanometer Copper/epoxy resin composite material of testing four preparations, the tensile strength of Nanometer Copper/epoxy resin composite material prepared by known test four is 49.840MPa, Young's modulus is 1697.242MPa, hardness is 83.67 °, with pure epoxy resin tensile strength 34.146MPa, Young's modulus 804.167MPa, hardness is 82.07 ° and compares and improved respectively 46%, 110% and 2%.
Claims (10)
1. a preparation method for Nanometer Copper/epoxy resin composite material, is characterized in that a kind of preparation method of Nanometer Copper/epoxy resin composite material specifically completes according to the following steps:
One, prepare copper nanoparticle: 1. under room temperature take distilled water as solvent, utilize ultrasonic method by CuSO
45H
2o dissolves completely, obtains CuSO
4the aqueous solution; 2. the CuSO 1. obtaining to step 1
4in the aqueous solution, add PVP, ultrasonic 30min～50min, obtains PVP/CuSO
4mixed aqueous solution; 3. under room temperature, hydrazine hydrate is mixed with distilled water, obtain hydrazine hydrate solution; 4. under room temperature take distilled water as solvent, after NaOH is dissolved completely, obtain NaOH solution; 5. PVP/the CuSO first 2. step 1 being obtained
4mixed aqueous solution joins in three neck round-bottomed flasks, then to the hydrazine hydrate solution that adds step 1 3. to obtain in three neck round-bottomed flasks, the NaOH solution that adds step 1 4. to obtain in the most backward three neck round-bottomed flasks, in temperature, be to stir 20min～25min under 65 ℃～75 ℃ and the rotating speed condition that is 250r/min～350r/min, then use distilled water filtering and washing 2h～3h, in vacuum tightness, be vacuum-drying 2h～4h under 0.08MPa～0.09MPa and room temperature condition again, obtain copper nanoparticle;
The CuSO of step 1 described in 1.
45H
2the quality of O and the volume ratio of distilled water are (0.125g～0.25g): 1mL;
Quality and the CuSO of the PVP of step 1 described in 2.
4the volume ratio of the aqueous solution is (0.0125g～0.025g): 1mL;
The volume of hydrazine hydrate and the volume ratio of distilled water of step 1 described in is 3. (3～5): 1;
The quality of NaOH and the volume ratio of distilled water of step 1 described in is 4. (0.2g～0.35g): 1mL;
PVP/the CuSO of step 1 described in 5.
4the volume of mixed aqueous solution and the volume ratio of hydrazine hydrate solution are (0.8～1.25): 1;
PVP/the CuSO of step 1 described in 5.
4the volume ratio of the volume of mixed aqueous solution and NaOH solution is (2～3): 1;
Two, disperse: the copper nanoparticle that 5. step 1 is obtained joins in epoxy resin, use mulser under the rotating speed of rotating speed 7000r/min～8000r/min, to carry out emulsion dispersion 5min～7min, obtain Nanometer Copper/epoxy resin composition;
The quality of the copper nanoparticle described in step 2 and the mass ratio of epoxy resin are (0.005～0.35): 1;
Three, prepare matrix material: the Nanometer Copper/epoxy resin composition 1. step 2 being obtained and solidifying agent be preheating 1.5h～2h under the condition of 55 ℃～65 ℃ respectively, obtains the solidifying agent after Nanometer Copper/epoxy resin composition and the preheating after preheating; 2. the solidifying agent after Nanometer Copper/epoxy resin composition and preheating after the preheating 1. step 3 being obtained is to stir 4min～5min under 90r/min～110r/min at rotating speed, obtains Nanometer Copper/epoxy prepolymer; 3. will scribble tetrafluoroethylene mould preheating 1.5h～2h at the temperature of 55 ℃～65 ℃ of high vacuum silicone grease, obtain the tetrafluoroethylene mould that scribbles high vacuum silicone grease of preheating; 4. Nanometer Copper/the epoxy prepolymer first 2. step 3 being obtained is poured step 3 into 3. in the tetrafluoroethylene mould that scribbles high vacuum silicone grease of preheating, then the tetrafluoroethylene mould that scribbles high vacuum silicone grease is put into baking oven and at 65 ℃～75 ℃ of temperature, solidified successively 2h～2.5h, in temperature, be at 120 ℃～130 ℃, to solidify 2h～3h, in temperature, be at 145 ℃～155 ℃, to solidify 1h～1.5h, obtain Nanometer Copper/epoxy resin composite material;
Step 3 1. described solidifying agent is Versamid;
The step 3 1. mass ratio of the epoxy resin described in quality and the step 2 of described solidifying agent is (0.4～0.5): 1.
2. the preparation method of a kind of Nanometer Copper/epoxy resin composite material according to claim 1, is characterized in that the CuSO described in step 1 1.
45H
2the quality of O and the volume ratio of distilled water are (0.15g～0.2g): 1mL.
3. the preparation method of a kind of Nanometer Copper/epoxy resin composite material according to claim 1, is characterized in that quality and the CuSO of the PVP described in step 1 2.
4the volume ratio of the aqueous solution is (0.015g～0.025g): 1mL.
4. the preparation method of a kind of Nanometer Copper/epoxy resin composite material according to claim 1, it is characterized in that the quality of the NaOH described in step 1 4. with the volume ratio of distilled water be (0.25g～0.35g): 1mL.
5. the preparation method of a kind of Nanometer Copper/epoxy resin composite material according to claim 1, is characterized in that the PVP/CuSO described in step 1 5.
4the volume of mixed aqueous solution and the volume ratio of hydrazine hydrate solution are (0.9～1.25): 1.
6. the preparation method of a kind of Nanometer Copper/epoxy resin composite material according to claim 1, is characterized in that the PVP/CuSO described in step 1 5.
4the volume ratio of the volume of mixed aqueous solution and NaOH solution is (2.5～3): 1.
7. the preparation method of a kind of Nanometer Copper/epoxy resin composite material according to claim 1, is characterized in that the quality of copper nanoparticle and the mass ratio of epoxy resin described in step 2 is (0.001～0.28): 1.
8. the preparation method of a kind of Nanometer Copper/epoxy resin composite material according to claim 1, Nanometer Copper/epoxy resin composition after the preheating that it is characterized in that during step 3 2., 1. step 3 being obtained and the solidifying agent after preheating are to stir 4.5min～5min under 95r/min～110r/min at rotating speed, obtain Nanometer Copper/epoxy prepolymer.
9. the preparation method of a kind of Nanometer Copper/epoxy resin composite material according to claim 1, it is characterized in that the Nanometer Copper/epoxy prepolymer first 2. step 3 being obtained during step 3 4. pours step 3 into 3. in the tetrafluoroethylene mould that scribbles high vacuum silicone grease of preheating, then the tetrafluoroethylene mould that scribbles high vacuum silicone grease is put into baking oven and at 68 ℃～75 ℃ of temperature, solidified successively 2h～2.5h, in temperature, be at 125 ℃～130 ℃, to solidify 2.5h～3h, in temperature, be at 150 ℃～155 ℃, to solidify 1h～1.5h, obtain Nanometer Copper/epoxy resin composite material.
10. the preparation method of a kind of Nanometer Copper/epoxy resin composite material according to claim 1, it is characterized in that step 3 1. the mass ratio of the epoxy resin described in quality and the step 2 of described solidifying agent be (0.45～0.5): 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310653506.8A CN103724938B (en) | 2013-12-06 | 2013-12-06 | A kind of preparation method of nano-copper/epoxy resin composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310653506.8A CN103724938B (en) | 2013-12-06 | 2013-12-06 | A kind of preparation method of nano-copper/epoxy resin composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103724938A true CN103724938A (en) | 2014-04-16 |
| CN103724938B CN103724938B (en) | 2015-10-21 |
Family
ID=50449251
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310653506.8A Expired - Fee Related CN103724938B (en) | 2013-12-06 | 2013-12-06 | A kind of preparation method of nano-copper/epoxy resin composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103724938B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530653A (en) * | 2014-12-26 | 2015-04-22 | 黑龙江大学 | Preparation method of epoxy resin/graphene/nano copper composite material |
| CN106818869A (en) * | 2017-01-10 | 2017-06-13 | 南通大学 | A kind of preparation method of carbon-based nano carbon/carbon-copper composite material |
| CN107267938A (en) * | 2017-05-16 | 2017-10-20 | 上海理工大学 | A kind of novel oxidation-resistant Nanometer Copper soldering paste and its preparation method and application |
| CN107685151A (en) * | 2017-08-28 | 2018-02-13 | 江西赣大材料技术研究有限公司 | A kind of preparation method of the compound antibacterial solid sols of nanometer of copper epoxy |
| CN107936295A (en) * | 2017-11-24 | 2018-04-20 | 广东聚航新材料研究院有限公司 | A kind of modified Nano copper and Nanometer Copper epoxy resin composite material and preparation method thereof |
| CN111922360A (en) * | 2020-10-19 | 2020-11-13 | 西安宏星电子浆料科技股份有限公司 | Preparation method of nano copper powder |
| CN113170785A (en) * | 2021-04-07 | 2021-07-27 | 华东师范大学 | Copper antibacterial composite material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408896A (en) * | 2013-05-21 | 2013-11-27 | 中国科学院深圳先进技术研究院 | Nano-copper-containing epoxide resin composite material and preparation method thereof |
-
2013
- 2013-12-06 CN CN201310653506.8A patent/CN103724938B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408896A (en) * | 2013-05-21 | 2013-11-27 | 中国科学院深圳先进技术研究院 | Nano-copper-containing epoxide resin composite material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 罗小虎等: "《利用PCB碱性蚀刻废液制备纳米铜导电胶》", 《电镀与涂饰》 * |
| 郑顺丽等: "《纳米复合导电性环氧树脂涂层的研究》", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530653A (en) * | 2014-12-26 | 2015-04-22 | 黑龙江大学 | Preparation method of epoxy resin/graphene/nano copper composite material |
| CN106818869A (en) * | 2017-01-10 | 2017-06-13 | 南通大学 | A kind of preparation method of carbon-based nano carbon/carbon-copper composite material |
| CN106818869B (en) * | 2017-01-10 | 2019-06-21 | 南通大学 | A kind of preparation method of carbon-based nano carbon/carbon-copper composite material |
| CN107267938A (en) * | 2017-05-16 | 2017-10-20 | 上海理工大学 | A kind of novel oxidation-resistant Nanometer Copper soldering paste and its preparation method and application |
| CN107267938B (en) * | 2017-05-16 | 2019-04-05 | 上海理工大学 | A kind of anti-oxidant Nanometer Copper soldering paste and its preparation method and application |
| CN107685151A (en) * | 2017-08-28 | 2018-02-13 | 江西赣大材料技术研究有限公司 | A kind of preparation method of the compound antibacterial solid sols of nanometer of copper epoxy |
| CN107936295A (en) * | 2017-11-24 | 2018-04-20 | 广东聚航新材料研究院有限公司 | A kind of modified Nano copper and Nanometer Copper epoxy resin composite material and preparation method thereof |
| WO2019101049A1 (en) * | 2017-11-24 | 2019-05-31 | 广东聚航新材料研究院有限公司 | Modified nano-copper, and nano-copper-epoxy resin composite material and manufacturing method therefor |
| CN111922360A (en) * | 2020-10-19 | 2020-11-13 | 西安宏星电子浆料科技股份有限公司 | Preparation method of nano copper powder |
| CN113170785A (en) * | 2021-04-07 | 2021-07-27 | 华东师范大学 | Copper antibacterial composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103724938B (en) | 2015-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103724938B (en) | A kind of preparation method of nano-copper/epoxy resin composite material | |
| Zhao et al. | Layer-by-layer grafting CNTs onto carbon fibers surface for enhancing the interfacial properties of epoxy resin composites | |
| JP6096806B2 (en) | Resin composition for electromagnetic shielding containing composite carbon material | |
| CN103725000B (en) | A kind of heat-resistant polymer base electro-magnetic screen function-graded material | |
| Wu et al. | Preparation of silver-plated carbon nanotubes/carbon fiber hybrid fibers by combining freeze-drying deposition with a sizing process to enhance the mechanical properties of carbon fiber composites | |
| KR101090729B1 (en) | Highly conductive resin composition having carbon composite | |
| CN104387671B (en) | A kind of preparation method of PA6/PP/ CNT High performance nanometer composite material | |
| CN105219018A (en) | A kind of preparation method of modified carbon fiber reinforced polyether ether ketone matrix material | |
| CN106120458B (en) | A kind of preparation method of polyimides conductive paper | |
| CN108659467A (en) | The method of SiC/ graphene oxide compound modification of epoxy resin | |
| JP2016065214A5 (en) | ||
| CN103408895A (en) | Preparation method of graphene/epoxy resin composite material | |
| CN109627689A (en) | A kind of preparation method of graphene-epoxy resin composite material | |
| CN104530653A (en) | Preparation method of epoxy resin/graphene/nano copper composite material | |
| Kang et al. | Multiwalled carbon nanotube pretreatment to enhance tensile properties, process stability, and filler dispersion of polyamide 66 nanocomposites | |
| CN111592737A (en) | Microwave-assisted efficient construction method for high-strength interface of carbon-based reinforcement/resin composite material | |
| CN104875395A (en) | Preparation method of forming material for selective laser sintering | |
| CN106700526A (en) | High-performance LCF/Ni/PA6 composite material with electromagnetic shielding function, and preparation method thereof | |
| CN105086363B (en) | The function modified method of composite based on co-curing and Polymerization induced phase separation | |
| Naveen et al. | Self-healing microcapsules encapsulated with carbon nanotubes for improved thermal and electrical properties | |
| Chen et al. | Synthesis and characterization of MC nylon/modified yttrium hydroxide nanocomposites | |
| Wu et al. | Improvements in interfacial and heat-resistant properties of carbon fiber/methylphenylsilicone resins composites by incorporating silica-coated multi-walled carbon nanotubes | |
| CN107163559A (en) | A kind of SLS strengthens nylon powder preparation technology with glass fiber powder | |
| CN106243622A (en) | Carbon nano-tube/poly ether ether ketone composite powder material and preparation method for SLS | |
| Yuan et al. | Self-healing and in-situ real-time damage-reporting fiber-reinforced composite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhao Dongyu Inventor after: Zhang Xiwen Inventor after: Yan Fei Inventor after: Han Chunhua Inventor after: Fu Jingwen Inventor after: Wang Lin Inventor before: Zhao Dongyu Inventor before: Yan Fei Inventor before: Han Chunhua Inventor before: Fu Jingwen Inventor before: Wang Lin Inventor before: Zhang Xiwen |
|
| COR | Change of bibliographic data | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151021 Termination date: 20181206 |