CN103724938B - A kind of preparation method of nano-copper/epoxy resin composite material - Google Patents
A kind of preparation method of nano-copper/epoxy resin composite material Download PDFInfo
- Publication number
- CN103724938B CN103724938B CN201310653506.8A CN201310653506A CN103724938B CN 103724938 B CN103724938 B CN 103724938B CN 201310653506 A CN201310653506 A CN 201310653506A CN 103724938 B CN103724938 B CN 103724938B
- Authority
- CN
- China
- Prior art keywords
- copper
- epoxy resin
- cuso
- preheating
- distilled water
- 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.)
- Expired - Fee Related
Links
Abstract
A preparation method for nano-copper/epoxy resin composite material, it relates to a kind of preparation method of epoxy resin composite material.The object of the invention is to solve existing nano-copper/epoxy resin composite material to there is copper nanoparticle and easily reunite, in the epoxy bad dispersibility and the low problem of the nano-copper/epoxy resin composite material mechanical property caused.Step: one, prepare copper nanoparticle; Two, disperse; Three, matrix material is prepared.Advantage: one, in nano-copper/epoxy resin composite material, copper powder is nano level; Two, the oxidation of copper nanoparticle is effectively prevented; Three, adopt mulser to Nanometer Copper/epoxy-resin systems dispersion, method is simple, good dispersity; Four, the tensile strength 38MPa ~ 50MPa of nano-copper/epoxy resin composite material for preparing of the present invention, Young's modulus 1200MPa ~ 1700MPa, hardness 80 ° ~ 84 °.The present invention can prepare 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 is a lot of outstanding performance, as the mechanical property of excellence, electrical insulation capability is good, and shrinking percentage is low, adhesiveproperties is good, chemical resistant properties, good processing characteristics, cheap etc., it is very extensive that these make it apply, and is widely used in the fields such as coating, sizing agent, electronic instrument, aerospace.But the cross-linking density after epoxy resin cure is large, in tridimensional network, there is the shortcomings such as matter is crisp, poor impact resistance, resistance to fatigue and thermotolerance are poor, internal stress is large, which greatly limits its application.And epoxy/nanocomposites is that most is great-hearted in type material now, the performance of some excellences of nanoparticle can effectively combine with epoxy resin by it, 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 the calorifics of raising epoxy resin cured product, optics, mechanics and electromagnetic property etc.
Copper nanoparticle is little owing to having size, and the large and feature such as quantum size effect and macro quanta tunnel effect of specific surface area, therefore has the property being different from block and macrobead copper material.And copper nanoparticle scattering problem is in the epoxy very scabrous, because copper nanoparticle is easily reunited, easily cause matrix material stress concentration, form defect in the composite, affect the mechanical property of matrix material.And mainly have several method for solution copper nanoparticle scattering problem in the epoxy at present: surface chemical modification, dispersant, ultrasonic disperse, mechanical dispersion and solvent dispersion.General some auxiliary agents of interpolation that adopt realize copper nanoparticle scattering problem in the epoxy at present, there is copper nanoparticle and easily reunite in current nano-copper/epoxy resin composite material, in the epoxy bad dispersibility and the low problem of the nano-copper/epoxy resin composite material mechanical property caused.
Summary of the invention
The object of the invention is to solve existing nano-copper/epoxy resin composite material to there is copper nanoparticle and easily reunite, bad dispersibility and the low problem of the nano-copper/epoxy resin composite material mechanical property caused in the epoxy, and a kind of preparation method of nano-copper/epoxy resin composite material is provided.
A kind of preparation method of nano-copper/epoxy resin composite material specifically completes according to the following steps:
One, copper nanoparticle is prepared: be 1. solvent with distilled water under room temperature, utilize ultrasonic method by CuSO
45H
2o dissolves completely, obtains CuSO
4the aqueous solution; 2. to the CuSO that 1. step one obtains
4add PVP in the aqueous solution, ultrasonic 30min ~ 50min, obtain PVP/CuSO
4mixed aqueous solution; 3. under room temperature, hydrazine hydrate is mixed with distilled water, obtain hydrazine hydrate solution; 4. take distilled water as solvent under room temperature, after being dissolved completely by NaOH, obtain NaOH solution; 5. PVP/the CuSO first 2. step one obtained
4mixed aqueous solution joins in three neck round-bottomed flasks, then in three neck round-bottomed flasks, add the hydrazine hydrate solution that 3. step one obtains, the NaOH solution that 4. step one obtains is added in the most backward three neck round-bottomed flasks, 20min ~ 25min is stirred under temperature is 65 DEG C ~ 75 DEG C and rotating speed is the condition of 250r/min ~ 350r/min, then distilled water filtering and washing 2h ~ 3h is used, vacuum-drying 2h ~ 4h under vacuum tightness is 0.08MPa ~ 0.09MPa and room temperature condition, obtains copper nanoparticle again;
Step one 1. described in CuSO
45H
2the quality of O and the volume ratio of distilled water are (0.125g ~ 0.25g): 1mL;
Step one 2. described in the quality of PVP and CuSO
4the volume ratio of the aqueous solution is (0.0125g ~ 0.025g): 1mL;
Step one 3. described in the volume of hydrazine hydrate and the volume ratio of distilled water be (3 ~ 5): 1;
Step one 4. described in NaOH quality be (0.2g ~ 0.35g): 1mL with the volume ratio of distilled water;
Step one 5. described in PVP/CuSO
4the volume of mixed aqueous solution and the volume ratio of hydrazine hydrate solution are (0.8 ~ 1.25): 1;
Step one 5. described in PVP/CuSO
4the volume of mixed aqueous solution and the volume ratio of NaOH solution are (2 ~ 3): 1;
Two, disperse: copper nanoparticle step one 5. obtained joins in epoxy resin, use mulser to carry out emulsion dispersion 5min ~ 7min under the rotating speed of rotating speed 7000r/min ~ 8000r/min, 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, matrix material is prepared: the Nanometer Copper/epoxy resin composition 1. step 2 obtained and solidifying agent be preheating 1.5h ~ 2h under the condition of 55 DEG C ~ 65 DEG C respectively, obtains the solidifying agent after the Nanometer Copper/epoxy resin composition after preheating and preheating; 2. Nanometer Copper/the epoxy resin composition after preheating step 3 1. obtained and the solidifying agent after preheating stir 4min ~ 5min under rotating speed is 90r/min ~ 110r/min, obtain Nanometer Copper/epoxy prepolymer; 3. will scribble Teflon mould preheating 1.5h ~ 2h at the temperature of 55 DEG C ~ 65 DEG C of high vacuum silicone grease, obtain the Teflon mould scribbling high vacuum silicone grease of preheating; 4. Nanometer Copper/the epoxy prepolymer first 2. step 3 obtained pour into step 3 3. preheating scribble in the Teflon mould of high vacuum silicone grease, then the Teflon mould scribbling high vacuum silicone grease is put into baking oven and at temperature 65 DEG C ~ 75 DEG C, solidify 2h ~ 2.5h successively, 2h ~ 3h is solidified at temperature is 120 DEG C ~ 130 DEG C, at temperature is 145 DEG C ~ 155 DEG C, solidifies 1h ~ 1.5h, obtains nano-copper/epoxy resin composite material;
The 1. described solidifying agent of step 3 is Versamid;
The mass ratio of the quality of solidifying agent that step 3 is 1. described and the epoxy resin described in step 2 is (0.4 ~ 0.5): 1.
Advantage of the present invention: one, in the nano-copper/epoxy resin composite material prepared of 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, effectively prevents the oxidation of copper nanoparticle; Three, adopt mulser to Nanometer Copper/epoxy-resin systems dispersion, 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 nano-copper/epoxy resin composite material mechanical property improves; Four, the tensile strength 38MPa ~ 50MPa of nano-copper/epoxy resin composite material for preparing of the present invention, Young's modulus 1200MPa ~ 1700MPa, hardness 80 ° ~ 84 °.
The present invention can prepare nano-copper/epoxy resin composite material.
Accompanying drawing explanation
Fig. 1 is the SEM figure that the nano-copper/epoxy resin composite material of test one preparation amplifies 1000 times;
Fig. 2 is the SEM figure that the nano-copper/epoxy resin composite material of test two preparation amplifies 1000 times;
Fig. 3 is the SEM figure that the nano-copper/epoxy resin composite material of test three preparation amplifies 1000 times;
Fig. 4 is the SEM figure that the nano-copper/epoxy resin composite material of test four preparation amplifies 1000 times.
Embodiment
Embodiment one: present embodiment is that a kind of preparation method of nano-copper/epoxy resin composite material specifically completes according to the following steps:
One, copper nanoparticle is prepared: be 1. solvent with distilled water under room temperature, utilize ultrasonic method by CuSO
45H
2o dissolves completely, obtains CuSO
4the aqueous solution; 2. to the CuSO that 1. step one obtains
4add PVP in the aqueous solution, ultrasonic 30min ~ 50min, obtain PVP/CuSO
4mixed aqueous solution; 3. under room temperature, hydrazine hydrate is mixed with distilled water, obtain hydrazine hydrate solution; 4. take distilled water as solvent under room temperature, after being dissolved completely by NaOH, obtain NaOH solution; 5. PVP/the CuSO first 2. step one obtained
4mixed aqueous solution joins in three neck round-bottomed flasks, then in three neck round-bottomed flasks, add the hydrazine hydrate solution that 3. step one obtains, the NaOH solution that 4. step one obtains is added in the most backward three neck round-bottomed flasks, 20min ~ 25min is stirred under temperature is 65 DEG C ~ 75 DEG C and rotating speed is the condition of 250r/min ~ 350r/min, then distilled water filtering and washing 2h ~ 3h is used, vacuum-drying 2h ~ 4h under vacuum tightness is 0.08MPa ~ 0.09MPa and room temperature condition, obtains copper nanoparticle again;
Step one 1. described in CuSO
45H
2the quality of O and the volume ratio of distilled water are (0.125g ~ 0.25g): 1mL;
Step one 2. described in the quality of PVP and CuSO
4the volume ratio of the aqueous solution is (0.0125g ~ 0.025g): 1mL;
Step one 3. described in the volume of hydrazine hydrate and the volume ratio of distilled water be (3 ~ 5): 1;
Step one 4. described in NaOH quality be (0.2g ~ 0.35g): 1mL with the volume ratio of distilled water;
Step one 5. described in PVP/CuSO
4the volume of mixed aqueous solution and the volume ratio of hydrazine hydrate solution are (0.8 ~ 1.25): 1;
Step one 5. described in PVP/CuSO
4the volume of mixed aqueous solution and the volume ratio of NaOH solution are (2 ~ 3): 1;
Two, disperse: copper nanoparticle step one 5. obtained joins in epoxy resin, use mulser to carry out emulsion dispersion 5min ~ 7min under the rotating speed of rotating speed 7000r/min ~ 8000r/min, 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, matrix material is prepared: the Nanometer Copper/epoxy resin composition 1. step 2 obtained and solidifying agent be preheating 1.5h ~ 2h under the condition of 55 DEG C ~ 65 DEG C respectively, obtains the solidifying agent after the Nanometer Copper/epoxy resin composition after preheating and preheating; 2. Nanometer Copper/the epoxy resin composition after preheating step 3 1. obtained and the solidifying agent after preheating stir 4min ~ 5min under rotating speed is 90r/min ~ 110r/min, obtain Nanometer Copper/epoxy prepolymer; 3. will scribble Teflon mould preheating 1.5h ~ 2h at the temperature of 55 DEG C ~ 65 DEG C of high vacuum silicone grease, obtain the Teflon mould scribbling high vacuum silicone grease of preheating; 4. Nanometer Copper/the epoxy prepolymer first 2. step 3 obtained pour into step 3 3. preheating scribble in the Teflon mould of high vacuum silicone grease, then the Teflon mould scribbling high vacuum silicone grease is put into baking oven and at temperature 65 DEG C ~ 75 DEG C, solidify 2h ~ 2.5h successively, 2h ~ 3h is solidified at temperature is 120 DEG C ~ 130 DEG C, at temperature is 145 DEG C ~ 155 DEG C, solidifies 1h ~ 1.5h, obtains nano-copper/epoxy resin composite material;
The 1. described solidifying agent of step 3 is Versamid;
The mass ratio of the quality of solidifying agent that step 3 is 1. described and the epoxy resin described in step 2 is (0.4 ~ 0.5): 1.
Present embodiment can prepare nano-copper/epoxy resin composite material.
Present embodiment step 3 1. in Nanometer Copper/epoxy resin composition that step 2 is obtained and solidifying agent preheating 1.5h ~ 2h under the condition of 55 DEG C ~ 65 DEG C; Step 3 2. in Nanometer Copper/epoxy resin composition after preheating that 1. step 3 is obtained and the solidifying agent object that stirs 4min ~ 5min under rotating speed is 90r/min ~ 110r/min be discharge the bubble wrapped up in the epoxy and solidifying agent is uniformly dispersed in Nanometer Copper/epoxy resin composition.
Present embodiment is reductive agent with hydrazine hydrate, produces nitrogen in reaction process, effectively prevents the oxidation of copper nanoparticle.
The advantage of present embodiment: one, in the nano-copper/epoxy resin composite material prepared of present embodiment copper powder size at nano level, dimensional stabilizing; Two, present embodiment take hydrazine hydrate as reductive agent, produces nitrogen in reaction process, effectively prevents the oxidation of copper nanoparticle; Three, adopt mulser to Nanometer Copper/epoxy-resin systems dispersion, 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 nano-copper/epoxy resin composite material mechanical property improves; Four, the tensile strength 38MPa ~ 50MPa of nano-copper/epoxy resin composite material for preparing of present embodiment, Young's modulus 1200MPa ~ 1700MPa, hardness 80 ° ~ 84 °.
Embodiment two: present embodiment and embodiment one difference are: step one 1. described in CuSO
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: step one 2. described in the quality of PVP and CuSO
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: step one 4. described in NaOH quality be (0.25g ~ 0.35g): 1mL with the volume ratio of distilled water.Other steps are identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four difference is: step one 5. described in PVP/CuSO
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: step one 5. described in PVP/CuSO
4the volume of mixed aqueous solution and the volume ratio of NaOH solution are (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: step step 3 2. in the Nanometer Copper/epoxy resin composition after preheating that 1. step 3 is obtained and the solidifying agent after preheating under rotating speed is 95r/min ~ 110r/min, stir 4.5min ~ 5min, 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: step 3 4. in Nanometer Copper/epoxy prepolymer of first 2. step 3 being obtained pour into step 3 3. preheating scribble in the Teflon mould of high vacuum silicone grease, then the Teflon mould scribbling high vacuum silicone grease is put into baking oven and at temperature 68 DEG C ~ 75 DEG C, solidify 2h ~ 2.5h successively, 2.5h ~ 3h is solidified at temperature is 125 DEG C ~ 130 DEG C, at temperature is 150 DEG C ~ 155 DEG C, solidifies 1h ~ 1.5h, obtains nano-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 mass ratio of the quality of solidifying agent that step 3 is 1. described and the epoxy resin described in step 2 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 nano-copper/epoxy resin composite material specifically completes according to the following steps:
One, copper nanoparticle is prepared: be 1. solvent with distilled water under room temperature, utilize ultrasonic method by CuSO
45H
2o dissolves completely, obtains CuSO
4the aqueous solution; 2. to the CuSO that 1. step one obtains
4add PVP in the aqueous solution, ultrasonic 50min, obtain PVP/CuSO
4mixed aqueous solution; 3. under room temperature, hydrazine hydrate is mixed with distilled water, obtain hydrazine hydrate solution; 4. take distilled water as solvent under room temperature, after being dissolved completely by NaOH, obtain NaOH solution; 5. PVP/the CuSO first 2. step one obtained
4mixed aqueous solution joins in three neck round-bottomed flasks, then in three neck round-bottomed flasks, add the hydrazine hydrate solution that 3. step one obtains, the NaOH solution that 4. step one obtains is added in the most backward three neck round-bottomed flasks, 20min is stirred under temperature is 70 DEG C and rotating speed is the condition of 300r/min, then distilled water filtering and washing 3h is used, vacuum-drying 4h under vacuum tightness is 0.09MPa and room temperature condition, obtains copper nanoparticle again;
Step one 1. described in CuSO
45H
2the quality of O and the volume ratio of distilled water are 0.125g:1mL;
Step one 2. described in the quality of PVP and CuSO
4the volume ratio of the aqueous solution is 0.0125g:1mL;
Step one 3. described in the volume of hydrazine hydrate and the volume ratio of distilled water be 3:1;
Step one 4. described in NaOH quality be 0.21g:1mL with the volume ratio of distilled water;
Step one 5. described in PVP/CuSO
4the volume of mixed aqueous solution and the volume ratio of hydrazine hydrate solution are 1.25:1;
Step one 5. described in PVP/CuSO
4the volume of mixed aqueous solution and the volume ratio of NaOH solution are 2.5:1;
Two, disperse: copper nanoparticle step one 5. obtained joins in epoxy resin, use mulser to carry out emulsion dispersion 5min ~ 7min under the rotating speed of rotating speed 7500r/min, 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, matrix material is prepared: the Nanometer Copper/epoxy resin composition 1. step 2 obtained and solidifying agent be preheating 2h under the condition of 60 DEG C respectively, obtains the solidifying agent after the Nanometer Copper/epoxy resin composition after preheating and preheating; 2. Nanometer Copper/the epoxy resin composition after preheating step 3 1. obtained and the solidifying agent after preheating stir 4min ~ 5min under rotating speed is 100r/min, obtain Nanometer Copper/epoxy prepolymer; 3. will scribble Teflon mould preheating 2h at the temperature of 60 DEG C of high vacuum silicone grease, obtain the Teflon mould scribbling high vacuum silicone grease of preheating; 4. Nanometer Copper/the epoxy prepolymer first 2. step 3 obtained pour into step 3 3. preheating scribble in the Teflon mould of high vacuum silicone grease, then the Teflon mould scribbling high vacuum silicone grease is put into baking oven and under temperature 70 C, solidify 2h successively, 2.5h is solidified at temperature is 125 DEG C, at temperature is 150 DEG C, solidifies 1h, obtains nano-copper/epoxy resin composite material;
The 1. described solidifying agent of step 3 is Versamid;
The mass ratio of the quality of solidifying agent that step 3 is 1. described and the epoxy resin described in step 2 is 0.5:1.
Scanning electron microscope is used to analyze nano-copper/epoxy resin composite material prepared by test one, as shown in Figure 1, Fig. 1 is the SEM figure that the nano-copper/epoxy resin composite material of test one preparation amplifies 1000 times, copper nanoparticle dispersiveness is in the epoxy better as can be seen from Figure 1, do not reunite, after adding appropriate copper nanoparticle, the section of matrix material becomes coarse injustice, certain interfacial interaction is had between visible copper nanoparticle and epoxy resin, can effectively prevent matrix material stress from concentrating the destruction caused, thus improve the mechanical property of epoxy resin.
The mechanical property of microcomputer control universal testing machine to nano-copper/epoxy resin composite material prepared by test one is used to test, the tensile strength of nano-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 improve 14%, 61% and 0.5% respectively.
Test two: a kind of preparation method of nano-copper/epoxy resin composite material specifically completes according to the following steps:
One, copper nanoparticle is prepared: be 1. solvent with distilled water under room temperature, utilize ultrasonic method by CuSO
45H
2o dissolves completely, obtains CuSO
4the aqueous solution; 2. to the CuSO that 1. step one obtains
4add PVP in the aqueous solution, ultrasonic 50min, obtain PVP/CuSO
4mixed aqueous solution; 3. under room temperature, hydrazine hydrate is mixed with distilled water, obtain hydrazine hydrate solution; 4. take distilled water as solvent under room temperature, after being dissolved completely by NaOH, obtain NaOH solution; 5. PVP/the CuSO first 2. step one obtained
4mixed aqueous solution joins in three neck round-bottomed flasks, then in three neck round-bottomed flasks, add the hydrazine hydrate solution that 3. step one obtains, the NaOH solution that 4. step one obtains is added in the most backward three neck round-bottomed flasks, 20min is stirred under temperature is 70 DEG C and rotating speed is the condition of 300r/min, then distilled water filtering and washing 3h is used, vacuum-drying 4h under vacuum tightness is 0.09MPa and room temperature condition, obtains copper nanoparticle again;
Step one 1. described in CuSO
45H
2the quality of O and the volume ratio of distilled water are 0.125g:1mL;
Step one 2. described in the quality of PVP and CuSO
4the volume ratio of the aqueous solution is 0.0125g:1mL;
Step one 3. described in the volume of hydrazine hydrate and the volume ratio of distilled water be 3:1;
Step one 4. described in NaOH quality be 0.21g:1mL with the volume ratio of distilled water;
Step one 5. described in PVP/CuSO
4the volume of mixed aqueous solution and the volume ratio of hydrazine hydrate solution are 1.25:1;
Step one 5. described in PVP/CuSO
4the volume of mixed aqueous solution and the volume ratio of NaOH solution are 2.5:1;
Two, disperse: copper nanoparticle step one 5. obtained joins in epoxy resin, use mulser to carry out emulsion dispersion 5min ~ 7min under the rotating speed of rotating speed 7500r/min, 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, matrix material is prepared: the Nanometer Copper/epoxy resin composition 1. step 2 obtained and solidifying agent be preheating 2h under the condition of 60 DEG C respectively, obtains the solidifying agent after the Nanometer Copper/epoxy resin composition after preheating and preheating; 2. Nanometer Copper/the epoxy resin composition after preheating step 3 1. obtained and the solidifying agent after preheating stir 4min ~ 5min under rotating speed is 100r/min, obtain Nanometer Copper/epoxy prepolymer; 3. will scribble Teflon mould preheating 2h at the temperature of 60 DEG C of high vacuum silicone grease, obtain the Teflon mould scribbling high vacuum silicone grease of preheating; 4. Nanometer Copper/the epoxy prepolymer first 2. step 3 obtained pour into step 3 3. preheating scribble in the Teflon mould of high vacuum silicone grease, then the Teflon mould scribbling high vacuum silicone grease is put into baking oven and under temperature 70 C, solidify 2h successively, 2.5h is solidified at temperature is 125 DEG C, at temperature is 150 DEG C, solidifies 1h, obtains nano-copper/epoxy resin composite material;
The 1. described solidifying agent of step 3 is Versamid;
The mass ratio of the quality of solidifying agent that step 3 is 1. described and the epoxy resin described in step 2 is 0.5:1.
Scanning electron microscope is used to analyze nano-copper/epoxy resin composite material prepared by test two, as shown in Figure 2, Fig. 2 is the SEM figure that the nano-copper/epoxy resin composite material of test two preparation amplifies 1000 times, copper nanoparticle dispersiveness is in the epoxy better as can be seen from Figure 2, do not reunite, after adding appropriate copper nanoparticle, the section of matrix material becomes coarse injustice, certain interfacial interaction is had between visible copper nanoparticle and epoxy resin, can effectively prevent matrix material stress from concentrating the destruction caused, thus improve the mechanical property of epoxy resin.
The mechanical property of microcomputer control universal testing machine to nano-copper/epoxy resin composite material prepared by test two is used to test, the tensile strength of nano-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 improve 21%, 77% and 0.8% respectively.
Test three: a kind of preparation method of nano-copper/epoxy resin composite material specifically completes according to the following steps:
One, copper nanoparticle is prepared: be 1. solvent with distilled water under room temperature, utilize ultrasonic method by CuSO
45H
2o dissolves completely, obtains CuSO
4the aqueous solution; 2. to the CuSO that 1. step one obtains
4add PVP in the aqueous solution, ultrasonic 50min, obtain PVP/CuSO
4mixed aqueous solution; 3. under room temperature, hydrazine hydrate is mixed with distilled water, obtain hydrazine hydrate solution; 4. take distilled water as solvent under room temperature, after being dissolved completely by NaOH, obtain NaOH solution; 5. PVP/the CuSO first 2. step one obtained
4mixed aqueous solution joins in three neck round-bottomed flasks, then in three neck round-bottomed flasks, add the hydrazine hydrate solution that 3. step one obtains, the NaOH solution that 4. step one obtains is added in the most backward three neck round-bottomed flasks, 20min is stirred under temperature is 70 DEG C and rotating speed is the condition of 300r/min, then distilled water filtering and washing 3h is used, vacuum-drying 4h under vacuum tightness is 0.09MPa and room temperature condition, obtains copper nanoparticle again;
Step one 1. described in CuSO
45H
2the quality of O and the volume ratio of distilled water are 0.125g:1mL;
Step one 2. described in the quality of PVP and CuSO
4the volume ratio of the aqueous solution is 0.0125g:1mL;
Step one 3. described in the volume of hydrazine hydrate and the volume ratio of distilled water be 3:1;
Step one 4. described in NaOH quality be 0.21g:1mL with the volume ratio of distilled water;
Step one 5. described in PVP/CuSO
4the volume of mixed aqueous solution and the volume ratio of hydrazine hydrate solution are 1.25:1;
Step one 5. described in PVP/CuSO
4the volume of mixed aqueous solution and the volume ratio of NaOH solution are 2.5:1;
Two, disperse: copper nanoparticle step one 5. obtained joins in epoxy resin, use mulser to carry out emulsion dispersion 5min ~ 7min under the rotating speed of rotating speed 7500r/min, 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, matrix material is prepared: the Nanometer Copper/epoxy resin composition 1. step 2 obtained and solidifying agent be preheating 2h under the condition of 60 DEG C respectively, obtains the solidifying agent after the Nanometer Copper/epoxy resin composition after preheating and preheating; 2. Nanometer Copper/the epoxy resin composition after preheating step 3 1. obtained and the solidifying agent after preheating stir 4min ~ 5min under rotating speed is 100r/min, obtain Nanometer Copper/epoxy prepolymer; 3. will scribble Teflon mould preheating 2h at the temperature of 60 DEG C of high vacuum silicone grease, obtain the Teflon mould scribbling high vacuum silicone grease of preheating; 4. Nanometer Copper/the epoxy prepolymer first 2. step 3 obtained pour into step 3 3. preheating scribble in the Teflon mould of high vacuum silicone grease, then the Teflon mould scribbling high vacuum silicone grease is put into baking oven and under temperature 70 C, solidify 2h successively, 2.5h is solidified at temperature is 125 DEG C, at temperature is 150 DEG C, solidifies 1h, obtains nano-copper/epoxy resin composite material;
The 1. described solidifying agent of step 3 is Versamid;
The mass ratio of the quality of solidifying agent that step 3 is 1. described and the epoxy resin described in step 2 is 0.5:1.
Scanning electron microscope is used to analyze nano-copper/epoxy resin composite material prepared by test three, as shown in Figure 3, Fig. 3 is the SEM figure that the nano-copper/epoxy resin composite material of test three preparation amplifies 1000 times, copper nanoparticle dispersiveness is in the epoxy better as can be seen from Figure 3, do not reunite, after adding appropriate copper nanoparticle, the section of matrix material becomes coarse injustice, certain interfacial interaction is had between visible copper nanoparticle and epoxy resin, can effectively prevent matrix material stress from concentrating the destruction caused, thus improve the mechanical property of epoxy resin.
The mechanical property of microcomputer control universal testing machine to nano-copper/epoxy resin composite material prepared by test three is used to test, the tensile strength of nano-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 improve 32%, 94% and 1.3% respectively.
Test four: a kind of preparation method of nano-copper/epoxy resin composite material specifically completes according to the following steps:
One, copper nanoparticle is prepared: be 1. solvent with distilled water under room temperature, utilize ultrasonic method by CuSO
45H
2o dissolves completely, obtains CuSO
4the aqueous solution; 2. to the CuSO that 1. step one obtains
4add PVP in the aqueous solution, ultrasonic 50min, obtain PVP/CuSO
4mixed aqueous solution; 3. under room temperature, hydrazine hydrate is mixed with distilled water, obtain hydrazine hydrate solution; 4. take distilled water as solvent under room temperature, after being dissolved completely by NaOH, obtain NaOH solution; 5. PVP/the CuSO first 2. step one obtained
4mixed aqueous solution joins in three neck round-bottomed flasks, then in three neck round-bottomed flasks, add the hydrazine hydrate solution that 3. step one obtains, the NaOH solution that 4. step one obtains is added in the most backward three neck round-bottomed flasks, 20min is stirred under temperature is 70 DEG C and rotating speed is the condition of 300r/min, then distilled water filtering and washing 3h is used, vacuum-drying 4h under vacuum tightness is 0.09MPa and room temperature condition, obtains copper nanoparticle again;
Step one 1. described in CuSO
45H
2the quality of O and the volume ratio of distilled water are 0.125g:1mL;
Step one 2. described in the quality of PVP and CuSO
4the volume ratio of the aqueous solution is 0.0125g:1mL;
Step one 3. described in the volume of hydrazine hydrate and the volume ratio of distilled water be 3:1;
Step one 4. described in NaOH quality be 0.21g:1mL with the volume ratio of distilled water;
Step one 5. described in PVP/CuSO
4the volume of mixed aqueous solution and the volume ratio of hydrazine hydrate solution are 1.25:1;
Step one 5. described in PVP/CuSO
4the volume of mixed aqueous solution and the volume ratio of NaOH solution are 2.5:1;
Two, disperse: copper nanoparticle step one 5. obtained joins in epoxy resin, use mulser to carry out emulsion dispersion 5min ~ 7min under the rotating speed of rotating speed 7500r/min, 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, matrix material is prepared: the Nanometer Copper/epoxy resin composition 1. step 2 obtained and solidifying agent be preheating 2h under the condition of 60 DEG C respectively, obtains the solidifying agent after the Nanometer Copper/epoxy resin composition after preheating and preheating; 2. Nanometer Copper/the epoxy resin composition after preheating step 3 1. obtained and the solidifying agent after preheating stir 4min ~ 5min under rotating speed is 100r/min, obtain Nanometer Copper/epoxy prepolymer; 3. will scribble Teflon mould preheating 2h at the temperature of 60 DEG C of high vacuum silicone grease, obtain the Teflon mould scribbling high vacuum silicone grease of preheating; 4. Nanometer Copper/the epoxy prepolymer first 2. step 3 obtained pour into step 3 3. preheating scribble in the Teflon mould of high vacuum silicone grease, then the Teflon mould scribbling high vacuum silicone grease is put into baking oven and under temperature 70 C, solidify 2h successively, 2.5h is solidified at temperature is 125 DEG C, at temperature is 150 DEG C, solidifies 1h, obtains nano-copper/epoxy resin composite material;
The 1. described solidifying agent of step 3 is Versamid;
The mass ratio of the quality of solidifying agent that step 3 is 1. described and the epoxy resin described in step 2 is 0.5:1.
Scanning electron microscope is used to analyze nano-copper/epoxy resin composite material prepared by test four, as shown in Figure 4, Fig. 4 is the SEM figure that the nano-copper/epoxy resin composite material of test four preparation amplifies 1000 times, copper nanoparticle dispersiveness is in the epoxy better as can be seen from Figure 4, do not reunite, after adding appropriate copper nanoparticle, the section of matrix material becomes coarse injustice, certain interfacial interaction is had between visible copper nanoparticle and epoxy resin, can effectively prevent matrix material stress from concentrating the destruction caused, thus improve the mechanical property of epoxy resin.
The mechanical property of microcomputer control universal testing machine to nano-copper/epoxy resin composite material prepared by test four is used to test, the tensile strength of nano-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 improve 46%, 110% and 2% respectively.
Claims (2)
1. a preparation method for nano-copper/epoxy resin composite material, is characterized in that what a kind of preparation method of nano-copper/epoxy resin composite material specifically completed according to the following steps:
One, copper nanoparticle is prepared: be 1. solvent with distilled water under room temperature, utilize ultrasonic method by CuSO
45H
2o dissolves completely, obtains CuSO
4the aqueous solution; 2. to the CuSO that 1. step one obtains
4add PVP in the aqueous solution, ultrasonic 30min ~ 50min, obtain PVP/CuSO
4mixed aqueous solution; 3. under room temperature, hydrazine hydrate is mixed with distilled water, obtain hydrazine hydrate solution; 4. take distilled water as solvent under room temperature, after being dissolved completely by NaOH, obtain NaOH solution; 5. PVP/the CuSO first 2. step one obtained
4mixed aqueous solution joins in three neck round-bottomed flasks, then in three neck round-bottomed flasks, add the hydrazine hydrate solution that 3. step one obtains, the NaOH solution that 4. step one obtains is added in the most backward three neck round-bottomed flasks, 20min ~ 25min is stirred under temperature is 65 DEG C ~ 75 DEG C and rotating speed is the condition of 250r/min ~ 350r/min, then distilled water filtering and washing 2h ~ 3h is used, vacuum-drying 2h ~ 4h under vacuum tightness is 0.08MPa ~ 0.09MPa and room temperature condition, obtains copper nanoparticle again;
Step one 1. described in CuSO
45H
2the quality of O and the volume ratio of distilled water are (0.15g ~ 0.2g): 1mL;
Step one 2. described in the quality of PVP and CuSO
4the volume ratio of the aqueous solution is (0.015g ~ 0.025g): 1mL;
Step one 3. described in the volume of hydrazine hydrate and the volume ratio of distilled water be (3 ~ 5): 1;
Step one 4. described in the quality of NaOH and the volume ratio of distilled water be (0.25g ~ 0.35g): 1mL;
Step one 5. described in PVP/CuSO
4the volume of mixed aqueous solution and the volume ratio of hydrazine hydrate solution are (0.9 ~ 1.25): 1;
Step one 5. described in PVP/CuSO
4the volume of mixed aqueous solution and the volume ratio of NaOH solution are (2.5 ~ 3): 1;
Two, disperse: copper nanoparticle step one 5. obtained joins in epoxy resin, use mulser to carry out emulsion dispersion 5min ~ 7min under the rotating speed of rotating speed 7000r/min ~ 8000r/min, 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, matrix material is prepared: the Nanometer Copper/epoxy resin composition 1. step 2 obtained and solidifying agent be preheating 1.5h ~ 2h under the condition of 55 DEG C ~ 65 DEG C respectively, obtains the solidifying agent after the Nanometer Copper/epoxy resin composition after preheating and preheating; 2. Nanometer Copper/the epoxy resin composition after preheating step 3 1. obtained and the solidifying agent after preheating stir 4.5min ~ 5min under rotating speed is 95r/min ~ 110r/min, obtain Nanometer Copper/epoxy prepolymer; 3. will scribble Teflon mould preheating 1.5h ~ 2h at the temperature of 55 DEG C ~ 65 DEG C of high vacuum silicone grease, obtain the Teflon mould scribbling high vacuum silicone grease of preheating; 4. Nanometer Copper/the epoxy prepolymer first 2. step 3 obtained pour into step 3 3. preheating scribble in the Teflon mould of high vacuum silicone grease, then the Teflon mould scribbling high vacuum silicone grease is put into baking oven and at temperature 68 DEG C ~ 75 DEG C, solidify 2h ~ 2.5h successively, 2.5h ~ 3h is solidified at temperature is 125 DEG C ~ 130 DEG C, at temperature is 150 DEG C ~ 155 DEG C, solidifies 1h ~ 1.5h, obtains nano-copper/epoxy resin composite material;
The 1. described solidifying agent of step 3 is Versamid;
The mass ratio of the quality of solidifying agent that step 3 is 1. described and the epoxy resin described in step 2 is (0.45 ~ 0.5): 1.
2. a preparation method for nano-copper/epoxy resin composite material, is characterized in that what a kind of preparation method of nano-copper/epoxy resin composite material specifically completed according to the following steps:
One, copper nanoparticle is prepared: be 1. solvent with distilled water under room temperature, utilize ultrasonic method by CuSO
4 .5H
2o dissolves completely, obtains CuSO
4the aqueous solution; 2. to the CuSO that 1. step one obtains
4add PVP in the aqueous solution, ultrasonic 50min, obtain PVP/CuSO
4mixed aqueous solution; 3. under room temperature, hydrazine hydrate is mixed with distilled water, obtain hydrazine hydrate solution; 4. take distilled water as solvent under room temperature, after being dissolved completely by NaOH, obtain NaOH solution; 5. PVP/the CuSO first 2. step one obtained
4mixed aqueous solution joins in three neck round-bottomed flasks, then in three neck round-bottomed flasks, add the hydrazine hydrate solution that 3. step one obtains, the NaOH solution that 4. step one obtains is added in the most backward three neck round-bottomed flasks, 20min is stirred under temperature is 70 DEG C and rotating speed is the condition of 300r/min, then distilled water filtering and washing 3h is used, vacuum-drying 4h under vacuum tightness is 0.09MPa and room temperature condition, obtains copper nanoparticle again;
Step one 1. described in CuSO
4 .5H
2the quality of O and the volume ratio of distilled water are 0.125g:1mL;
Step one 2. described in the quality of PVP and CuSO
4the volume ratio of the aqueous solution is 0.0125g:1mL;
Step one 3. described in the volume of hydrazine hydrate and the volume ratio of distilled water be 3:1;
Step one 4. described in the quality of NaOH and the volume ratio of distilled water be 0.21g:1mL;
Step one 5. described in PVP/CuSO
4the volume of mixed aqueous solution and the volume ratio of hydrazine hydrate solution are 1.25:1;
Step one 5. described in PVP/CuSO
4the volume of mixed aqueous solution and the volume ratio of NaOH solution are 2.5:1;
Two, disperse: copper nanoparticle step one 5. obtained joins in epoxy resin, use mulser to carry out emulsion dispersion 5min ~ 7min under the rotating speed of rotating speed 7500r/min, 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, matrix material is prepared: the Nanometer Copper/epoxy resin composition 1. step 2 obtained and solidifying agent be preheating 2h under the condition of 60 DEG C respectively, obtains the solidifying agent after the Nanometer Copper/epoxy resin composition after preheating and preheating; 2. Nanometer Copper/the epoxy resin composition after preheating step 3 1. obtained and the solidifying agent after preheating stir 4min ~ 5min under rotating speed is 100r/min, obtain Nanometer Copper/epoxy prepolymer; 3. will scribble Teflon mould preheating 2h at the temperature of 60 DEG C of high vacuum silicone grease, obtain the Teflon mould scribbling high vacuum silicone grease of preheating; 4. Nanometer Copper/the epoxy prepolymer first 2. step 3 obtained pour into step 3 3. preheating scribble in the Teflon mould of high vacuum silicone grease, then the Teflon mould scribbling high vacuum silicone grease is put into baking oven and under temperature 70 C, solidify 2h successively, 2.5h is solidified at temperature is 125 DEG C, at temperature is 150 DEG C, solidifies 1h, obtains nano-copper/epoxy resin composite material;
The 1. described solidifying agent of step 3 is Versamid;
The mass ratio of the quality of solidifying agent that step 3 is 1. described and the epoxy resin described in step 2 is 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 CN103724938A (en) | 2014-04-16 |
| CN103724938B true 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) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530653B (en) * | 2014-12-26 | 2016-09-21 | 黑龙江大学 | A kind of preparation method of epoxy resin/graphite alkene/Nanometer Copper composite |
| 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 |
| 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 |
| CN111922360B (en) * | 2020-10-19 | 2021-01-01 | 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 |
|---|
| 《利用PCB碱性蚀刻废液制备纳米铜导电胶》;罗小虎等;《电镀与涂饰》;20130815;第32卷(第8期);第34页1.2.1-1.2.2 * |
| 《纳米复合导电性环氧树脂涂层的研究》;郑顺丽等;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20130415;第4页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103724938A (en) | 2014-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103724938B (en) | A kind of preparation method of nano-copper/epoxy resin composite material | |
| 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 | |
| CN106120458B (en) | A kind of preparation method of polyimides conductive paper | |
| Jang et al. | Effects of carbon fiber modification with multiwall CNT on the electrical conductivity and EMI shielding effectiveness of polycarbonate/carbon fiber/CNT composites | |
| CN104387671B (en) | A kind of preparation method of PA6/PP/ CNT High performance nanometer composite material | |
| CN104530653A (en) | Preparation method of epoxy resin/graphene/nano copper composite material | |
| CN106930100A (en) | A kind of preparation method of polyimides/graphene oxide complex fiber material | |
| Wang et al. | A high-performance thermally conductive and electrically insulating silver@ siloxane/graphene/epoxy composites at low filler content: Fabrication, mechanism study of insulation and thermal conductivity enhancement | |
| CN103408895A (en) | Preparation method of graphene/epoxy resin composite material | |
| Kang et al. | Multiwalled carbon nanotube pretreatment to enhance tensile properties, process stability, and filler dispersion of polyamide 66 nanocomposites | |
| Peighambardoust et al. | Electrically conductive epoxy‐based nanocomposite adhesives loaded with silver‐coated copper and silver‐coated reduced graphene oxide nanoparticles | |
| CN109627689A (en) | A kind of preparation method of graphene-epoxy resin composite material | |
| 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 | |
| CN102634208B (en) | Nanocomposite modification method applied to bismaleimide resin based composite | |
| CN109897341B (en) | Composite material of modified graphene reinforced epoxy resin and preparation method | |
| Han et al. | Influence of multi‐walled carbon nanotube content on electromagnetic wave absorption and mechanical properties of carbon nanotube/polyamide 12 composite | |
| Chen et al. | Synthesis and characterization of MC nylon/modified yttrium hydroxide nanocomposites | |
| Naveen et al. | Self-healing microcapsules encapsulated with carbon nanotubes for improved thermal and electrical properties | |
| CN109056336A (en) | Aqueous sizing agent of a kind of carbon fiber Wesy heat resistant type and its preparation method and application | |
| CN105086363A (en) | Composite material function modification method based on co-curing and reaction inductive phase separation | |
| CN104774455A (en) | Carbon nanotube modified nylon 612 antistatic composite material and preparation method thereof |
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 |
Granted publication date: 20151021 Termination date: 20181206 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |