CN111799012B - Antioxidant copper material and preparation method thereof - Google Patents
Antioxidant copper material and preparation method thereof Download PDFInfo
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- CN111799012B CN111799012B CN202010578213.8A CN202010578213A CN111799012B CN 111799012 B CN111799012 B CN 111799012B CN 202010578213 A CN202010578213 A CN 202010578213A CN 111799012 B CN111799012 B CN 111799012B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
Abstract
The invention discloses an antioxidant copper material and a preparation method thereof. The mercaptan compound is adsorbed on the surface of the copper material modified by the formate radical to form a self-assembled film, so that the corrosion resistance of the copper material is further enhanced. On the basis that the thermal stability of the copper material is improved by formic acid, the hydrophobic property of the copper material can be obviously improved by introducing the modification of mercaptan, so that a more stable hydrophobic oxidation-resistant layer is formed on the surface of the copper material. In addition, the modification process of the copper material can obviously improve the oxidation resistance of the copper material only by opening the environment of a common container and in a short time. The invention has simple preparation and low cost, and can realize effective oxidation-resistant and corrosion-resistant treatment on the copper-containing material.
Description
Technical Field
The invention belongs to the field of preparation of conductive materials, and particularly relates to an antioxidant copper material and a preparation method thereof.
Background
Copper, which is a metal material having both high conductivity and low cost, is widely used in various fields such as the electrical and power industry, the mechanical manufacturing industry, the chemical industry, the construction industry, the defense industry, and the like, and is a key material for manufacturing conductive paste, radio frequency identification RFID antennas, sensors, solar cells, display panels, electronic switches, electrode circuits, motor accessories, and the like. However, copper materials are very easily oxidized in air, and the surface of the copper materials is easily corroded, so that the conductivity of the copper materials is greatly reduced, and the application of the copper materials is limited. Therefore, the anti-oxidation technology of the copper material becomes the current research hotspot.
For example, CN 108084799A discloses a material for RFID antenna conductive patterns, which comprises the following steps of preparing Cu nanoparticles, coating an Ag layer on the Cu surface, preparing silver-coated copper nanoparticles, adding a solvent to prepare a conductive paste, coating the conductive paste on a flexible substrate by steel mesh printing, and sintering to obtain the desired antenna conductive patterns. The scheme avoids the oxidation of Cu nanoparticles by wrapping the Ag layer, and cannot reduce the cost of the conductive paste to the maximum extent.
For example, CN 104900297A discloses a copper conductive paste and a preparation method thereof, the prepared copper conductive paste is discharged and stored under a low-temperature vacuum condition of 0-8 ℃, and the conductive circuit needs to be subjected to inert atmosphere or vacuum sintering for 1 hour at a temperature range lower than 150 ℃. In order to prevent the oxidation of copper, the storage of the slurry and the sintering of the circuit are carried out under special conditions, and the sintering time is long.
For example, CN 107460464A discloses a surface treatment method for copper-containing materials, which modifies or adsorbs formate on the surface of the copper material to enhance the oxidation resistance of the copper material. The method comprises the following steps of mixing a copper-containing material with a polar solvent, adding a stabilizer and an auxiliary agent, carrying out sealed pressure reaction, and then carrying out liquid-solid separation, washing and drying to complete the anti-oxidation surface treatment of the copper material. The scheme needs to carry out reaction in a sealed and pressurized environment, and the oxidation-resistant copper material with good conductivity can be obtained.
Therefore, a simple, efficient and low-cost copper material antioxidant technology needs to be developed to solve the application problem in the fields of conductive paste, RFID tags, electrical switches, power engineering and the like.
Disclosure of Invention
In order to solve the defects of complex process, poor antioxidant effect and high preparation cost in the prior art, the invention aims to provide an antioxidant copper material and a preparation method thereof, and the preparation method has the advantages of simple preparation process, good antioxidant performance and low cost. The antioxidant copper material provided by the invention can be used for preparing antioxidant conductive paste with high conductivity, namely antioxidant copper paste.
The first aspect of the invention provides an antioxidant copper material, which is a copper material with the surface modified with formate and mercaptan; the mercaptan is adsorbed on the surface of the copper material modified by the formate.
The second aspect of the invention provides a preparation method of an antioxidant copper material, which comprises the following steps:
adding 1-15 mol/L formate solution and solvent into a first container, stirring uniformly to obtain a mixed solution, placing the copper material into the first container containing the mixed solution, reacting at 80-180 ℃ for 0.5-24 h, pouring out supernatant, adding 1.0 multiplied by 10 -4 ～1.0×10 -1 And (3) reacting the mercaptan in mol/L for 0.5-30 min, and then carrying out liquid-solid separation, washing and drying treatment to obtain the antioxidant copper material.
Further, the formate is at least one selected from lithium formate, sodium formate, magnesium formate, aluminum trimethyl formate, potassium formate, ammonium formate, calcium formate, zinc formate, iron formate, copper formate, barium formate, beryllium formate, nickel formate, cobalt formate and manganese formate; the solvent comprises an alcohol solution and oleylamine or n-octylamine or dodecylamine or n-tridecylamine or dodecyl dimethyl tertiary amine or octadecyl amine; the thiol is preferably at least one of methyl thiol, ethyl thiol, ethanedithiol, dodecyl thiol, hexadecyl thiol, 1-propyl thiol, 1, 3-propanedithiol, mercaptoethanol, cysteine, glutathione, and mercaptoethylamine.
Further, the copper material is selected from one of copper powder, copper nanowires, copper foils, copper wires and copper cables, but not limited thereto; the particle size of the copper powder is 10 nm-20 mu m.
Further, the mass ratio of the formate solution to the copper material is 5: 1-1: 5, and the mass ratio of the solvent to the copper material is 5: 1-100: 1; the mass ratio of the mercaptan to the copper material is 5: 1-50: 1. The mass ratio of the alcohol solution in the solvent to the oleylamine or the n-octylamine or the dodecylamine or the n-tridecylamine or the dodecyl dimethyl tertiary amine or the octadecyl amine is 5: 1-30: 1.
A third aspect of the present invention is to provide a conductive paste comprising 50 to 80wt% of the copper material for oxidation resistance of the present invention, 9 to 11wt% of a resin, and the balance of a curing agent.
Further, the resin is at least one of phenolic resin, epoxy resin, amino resin, polyester resin, polyurethane, silicone resin and polyacrylic resin, but not limited thereto; the curing agent is at least one of triethanolamine, phenol aldehyde amine, amine chloride, methyl ethyl ketone peroxide, diethylenetriamine and isocyanate, but not limited thereto.
A fourth aspect of the present invention is to provide a method of preparing a conductive paste, comprising the steps of:
(1) Taking the antioxidant copper material;
(2) And (2) adding the antioxidant copper material, the resin and the curing agent in the step (1) into a second container, and stirring and dispersing for 5-10 min at room temperature in a common environment to obtain the conductive paste.
The fifth aspect of the invention provides a conductive paste for an RFID tag, wherein a tag antenna of the RFID tag is made of the conductive paste provided by the invention or the conductive paste obtained by the method for preparing a conductive paste provided by the invention.
Further, the tag antenna is transferred to the substrate by the conductive paste through screen printing, ink-jet printing or gravure printing for curing, wherein the curing temperature is 80-200 ℃, and the curing time is 20 s-5 min.
Furthermore, the port of the IC chip of the RFID tag is solidified and bound with the tag antenna through the conductive paste, and the RFID tag with oxidation resistance and stable performance can be obtained.
By adopting the technical scheme, the invention has the beneficial effects that:
1. the anti-oxidation copper material is modified by formate and mercaptan together, and the mercaptan compound is adsorbed on the surface of the copper material modified by the formate to form a self-assembled film, so that the corrosion resistance of the copper material is further improved. On the basis that the formic acid radical improves the thermal stability of the copper material, the hydrophobic property of the copper material is greatly improved by modifying the mercaptan, so that a more stable hydrophobic oxidation resistant layer is formed on the surface of the copper material.
2. Compared with the copper-containing material subjected to double treatment of formate and mercaptan, the copper-containing material subjected to double treatment of formate and mercaptan disclosed by the invention has stronger oxidation resistance (including high-temperature oxidation resistance), saline-alkali corrosion resistance and higher conductivity, and can be applied to the application fields of copper-containing materials such as copper-based conductive paste, transparent conductive films containing copper nanowires, copper foils, copper cables, RFID antennas and the like.
3. The modification process of the copper material can realize good modification effect only in common environment and in a short time, is simple to operate, and has no strict experimental requirement on whether to isolate oxygen/air.
4. The invention has low cost and environmental protection, and can realize effective oxidation-resistant and corrosion-resistant treatment on copper-containing materials.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention, are incorporated in and constitute a part of this specification. In the drawings:
fig. 1 is a flow chart of a preparation method of the antioxidant copper material of the invention.
Fig. 2a is a surface contact angle test chart of copper foil without modification.
Fig. 2b is a surface contact angle test chart of the copper foil after only thiol modification.
Fig. 2c is a test chart of the surface contact angle of the copper foil modified by only formate.
Fig. 2d is a contact angle test chart of the copper foil surface modified by both formate and thiol provided in example 3.
Fig. 3a is an optical photograph of untreated copper foil after 24h salt spray experiment.
Fig. 3b is an optical photograph of the copper foil co-modified with formate and thiol provided in example 3 after a 24-hour salt spray experiment.
Fig. 4a is an optical photograph of an untreated copper wire after a 24h salt spray experiment.
Fig. 4b is an optical photograph of the copper wire co-modified with formate and thiol provided in example 4 after 24h salt spray experiment.
FIG. 5a is an SEM image of untreated plain copper powder after soaking in 0.1M NaOH solution for 10 h.
FIG. 5b is an SEM image of the antioxidant copper powder co-modified with formate and thiol provided in example 5 after being soaked in 0.1M NaOH solution for 10 h.
FIG. 6 is a comparative XRD plot of the copper powder provided in example 5 and untreated, conventional copper powder after immersion in 0.1M NaOH solution for 10 hours.
Fig. 7a is an SEM image of untreated plain copper powder after 24h salt spray experiments.
Fig. 7b is an SEM image of the antioxidant copper powder co-modified with formate and thiol provided in example 5 after 24h salt spray experiment.
Fig. 8 is a flow chart of a method for preparing the conductive paste according to the present invention.
Detailed Description
Specific structural and functional details disclosed herein are merely representative and are presented for purposes of describing example embodiments of the present invention. The present invention may be embodied in many alternate forms and should not be construed as limited to only the embodiments set forth herein.
As shown in table 1, a resistivity comparison table of the cured conductive paste obtained by the different embodiments is shown. As can be seen from Table 1, the co-modification of copper powder (average particle size 5 μm) with formate and mercaptan resulted in a mercaptan concentration of less than 1.0X 10 -4 At mol/L, the resistivity of the slurry begins to obviously increase, because the hydrophobic oxidation-resistant layer formed on the surface of the copper material is not compact enough when the formate and the mercaptan with lower concentration are jointly modified; when the concentration of mercaptan exceeds 1.0X 10 -1 At mol/L, the resistivity of the slurry also begins to rise remarkably, because the higher concentration of mercaptan replaces part of the formate to be adsorbed on the surface of the copper material, so that the thermal stability of the copper powder is reduced, the contact resistance is increased, and the conductivity of the slurry is greatly reduced in the subsequent curing process. Thus, the concentration of formate is 1.0X 10 -4 ～1.0×10 -1 The common modification effect of the mol/L mercaptan on the copper material is optimal.
TABLE 1 comparison of resistivities of conductive pastes modified with formate and different concentrations of thiol
As shown in table 2, a table comparing the resistivity of different conductive pastes after curing. By comparing the resistivity of the conductive paste prepared from the copper material modified by the formate or the thiol alone with the resistivity of the conductive paste prepared from the copper material modified by the formate and the thiol together provided by the invention, the following results can be obtained: under the condition of common open equipment, the resistivity of the conductive paste prepared by the copper material jointly modified by the formate and the mercaptan provided by the invention is 0.8 multiplied by 10 -6 ～1.5×10 -6 Omega m, and the resistivity of the conductive paste made of the copper material modified by the formate group is 1.0 multiplied by 10 -5 ～1.0×10 -4 Omega. M, resistivity of conductive paste made of copper material modified with thiol only, 1.2X 10 -4 ～3.5×10 -4 Omega.m. Compared with the prior art, the conductive paste provided by the invention has lower resistivity and better conductivity. Meanwhile, compared with the resistivity of the conductive paste prepared from the copper material independently modified by formate or mercaptan and prepared in a closed pressure-resistant container and the resistivity of the conductive paste provided by the invention, the resistivity of the conductive paste provided by the invention is lower, and the conductive effect is better.
Table 2 comparison table of resistivity after curing of different conductive pastes
Table 3 shows a comparison table of the resistivity of different conductive pastes after being left in air for 30 days. As can be seen from Table 2, the resistivity of the unmodified copper paste, the thiol-modified copper paste and the formate-modified copper paste after being left in the air for 30 days was 1.3X 10 -1 Ω·m、5.4×10 -4 Ω·m、1.3×10 -5 Omega.m, and the resistivity of the conductive paste provided by the invention after being placed in the air for 30 days is 1.5 multiplied by 10 -6 Omega.m. Namely the present inventionThe resistivity of the provided conductive paste after being placed in the air for 30 days is obviously different from the resistivity of the other copper pastes after being placed in the air for 30 days, which shows that the antioxidant effect of the conductive paste provided by the invention is obviously improved compared with the other copper pastes.
TABLE 3 comparison of resistivities of different conductive pastes in air before and after 30 days
| Categories | Resistivity before standing (omega. M) | Resistivity after standing (omega. M) |
| Unmodified copper slurry | 1.0×10 -4 | 1.3×10 -1 |
| Thiol-modified copper pastes | 7.7×10 -5 | 5.4×10 -4 |
| Copper paste modified only with formate | 2.9×10 -6 | 1.3×10 -5 |
| Copper paste modified by formate and mercaptan together | 0.8×10 -6 | 1.5×10 -6 |
The data comparison in tables 2 and 3 shows that the antioxidant copper material provided by the invention can be prepared only in a common open container, and the preparation condition is simple and environment-friendly. The conductive paste provided by the invention has the advantages of low resistivity, long-term stability and low cost. The invention can solve the limitation and defect of common copper materials and copper slurry in practical application, and can be widely applied to the fields of RFID labels, electric power industry and the like.
Preferred embodiments of the present invention are described in further detail below with reference to the accompanying drawings.
Example 1
2g of spherical copper powder with the particle size of 10nm are weighed. 20mL of butanol, 1.5mL of oleylamine, and 2mL of a potassium formate solution were added to the vessel and stirred well. Then, the copper powder was placed in a container containing the above mixed solution and heated and stirred at 80 ℃ for 1 hour. After natural cooling, the supernatant was decanted off and 20mL of 1.0X 10 -1 The mercaptoethanol in mol/L is stirred for 30s. And carrying out suction filtration and drying to obtain the antioxidant copper powder. Adding 0.4g of amino resin and 0.6g of ammonium chloride mixed solvent into the obtained antioxidant copper powder, and uniformly stirring for 5min at normal temperature in a natural environment to obtain conductive slurry with the resistivity of 1.4 multiplied by 10 -6 Ω·m。
Example 2
Weighing 2g of flake copper powder with the particle size of 500 nm. 30mL of propylene glycol, 1mL of n-octylamine and 1mL of magnesium formate solution are added to a container and stirred uniformly. Then the washed copper powder is placed in a container containing the mixed solution and heated and stirred for 3 hours at the temperature of 100 ℃. After natural cooling, the supernatant was decanted off and 20mL of 1.0X 10 -3 The mol/L cysteine was stirred for 10min. And carrying out suction filtration and drying to obtain the antioxidant copper powder co-modified by formate and mercaptan. Adding 0.3g of epoxy resin and 0.7g of phenolic aldehyde amine mixed solvent into the modified copper powder, and uniformly stirring for 6min in a natural environment at normal temperature to obtain the conductive slurry with the resistivity of 1.2 multiplied by 10 -6 Ω·m。
Example 3
Taking a piece of copper foil with the thickness of 18 mu m, performing ultrasonic treatment in glacial acetic acid for 10min, and washing surface impurities and impuritiesDrying the organic matters for later use. 30mL of ethylene glycol, 2mL of dodecylamine and 3mL of sodium formate solution are added into a container and stirred uniformly. Then, the washed copper foil was placed in a container containing the above mixed solution and heated and left standing at 120 ℃ for 1.5 hours. After natural cooling, the supernatant was decanted off and 30mL of a 1.0X 10 solution was added -2 The mol/L dodecanethiol is allowed to stand for 1min. Taking out the copper foil and drying the copper foil to obtain the antioxidant copper foil co-modified by formate and mercaptan, and immediately testing the resistivity to be 1.8 multiplied by 10 -8 Omega. M. The resistivity of the alloy is still 1.8 multiplied by 10 after the alloy is exposed in the air for 30 days -8 Ω·m。
Referring to fig. 2a, 2b, 2c and 2d, fig. 2a is a surface contact angle test chart of the copper foil without modification. In fig. 2a, the contact angle of the surface of the untreated copper foil is shown to be 101.1 °. Fig. 2b is a surface contact angle test chart of the copper foil after only thiol modification. In fig. 2b, the contact angle of the copper foil surface after thiol modification alone is shown to rise from 101.1 ° to 117.9 °. Fig. 2c is a test chart of the surface contact angle of the copper foil modified by only formate. In fig. 2c, it is shown that the contact angle of the copper foil surface after only formate modification decreases from 101.1 ° to 76.5 °. Fig. 2d is a contact angle test chart of the copper foil surface modified by both formate and thiol provided in example 3. In fig. 2d, the contact angle of the copper foil surface modified with both formate and thiol is shown to rise to a maximum of 133.5 °. Therefore, the common modification of the formate and the mercaptan can obviously improve the hydrophobic property of the surface of the copper material, so that a hydrophobic oxidation resistant layer is formed on the surface of the copper material.
Referring to fig. 3a and 3b, fig. 3a is an optical photograph of an untreated copper foil after a 24-hour salt spray experiment, and fig. 3b is an optical photograph of a copper foil which is provided in example 3 and is subjected to a 24-hour salt spray experiment after formate and thiol co-modification. The comparison shows that the untreated copper foil is dark in color, indicating that it has been oxidized; the oxidation-resistant copper foil provided by the invention still maintains the original metal color, which shows that the oxidation-resistant copper foil has good salt corrosion resistance.
Example 4
Weighing copper wire with diameter of 2.5mm and length of 80cm, winding into spring shape, and ultrasonically washing surface impurities and organic substances with glacial acetic acid for 10minDrying the mixture for later use. 30mL of glycerol, 3mL of n-tridecylamine and 4mL of ammonium formate solution were added to the vessel and stirred uniformly. Then, the washed copper wire was placed in a vessel containing the above mixed solution, heated at 150 ℃ and left to stand for 6 hours. After natural cooling, the supernatant was decanted off and 50mL of 1.0X 10 -4 The hexadecanethiol in mol/L is left to stand for 6min. Taking out and drying to obtain the antioxidant copper wire co-modified by formate and mercaptan, and immediately testing the resistivity to be 1.7 multiplied by 10 -8 Omega.m. The resistivity of the film after being exposed in the air for 30 days is still 1.7 multiplied by 10 -8 Ω·m。
Referring to fig. 4a and 4b, fig. 4a is an optical photograph of an untreated copper wire subjected to a 24h salt spray experiment, and fig. 4b is an optical photograph of a copper wire subjected to co-modification of formate and thiol provided in example 4 subjected to a 24h salt spray experiment. The comparison shows that the untreated copper wire has rough surface, black color and oxidized, which indicates that the wire does not have salt corrosion resistance; the surface of the oxidation-resistant copper wire provided by the invention is smooth and has metallic luster, which shows that the oxidation-resistant copper wire has good salt corrosion resistance.
Example 5
Weighing 2g of spherical copper powder with the particle size of 5 mu m, ultrasonically washing surface impurities and organic matters with glacial acetic acid for 10min, and carrying out suction filtration for later use. 40mL of glycerol, 1mL of dodecyldimethyl tertiary amine and 2mL of calcium formate solution are added to a container and stirred uniformly. Then the washed copper powder is placed in a container containing the mixed solution to be heated and stirred for 12 hours at 180 ℃. After natural cooling, the supernatant was decanted off and 20mL of 1.0X 10 -2 Stirring with mercaptoethylamine in a mol/L manner for 4min. And carrying out suction filtration and drying to obtain the antioxidant copper powder co-modified by formate and mercaptan. Adding 0.4g of phenolic resin and 0.6g of triethanolamine into the modified copper powder, and uniformly stirring for 9min in a natural environment at normal temperature to obtain the conductive slurry with the resistivity of 0.8 multiplied by 10 -6 Ω·m。
Referring to fig. 5a and 5b, fig. 5a is an SEM image of untreated ordinary copper powder after being soaked in 0.1M NaOH solution for 10h, and fig. 5b is an SEM image of antioxidant copper powder co-modified with formate and thiol provided in example 5 after being soaked in 0.1M NaOH solution for 10 h. The comparison shows that the surface of the antioxidant copper powder provided by the invention is smooth and flat, and the antioxidant copper powder has good alkali corrosion resistance.
Referring to fig. 6, fig. 6 is a XRD comparison graph of the antioxidant copper powder provided in example 5 and untreated common copper powder after soaking in 0.1M NaOH solution for 10 h. The comparison shows that the anti-oxidation copper powder provided by the invention hardly generates diffraction peaks of copper oxides, which shows that the anti-oxidation copper powder has stronger anti-oxidation performance.
Referring to fig. 7a and 7b, fig. 7a is an SEM image of untreated ordinary copper powder after 24h salt spray experiment, and fig. 7b is an SEM image of antioxidant copper powder co-modified by formate and thiol provided in example 5 after 24h salt spray experiment. The comparison shows that the antioxidant copper powder provided by the invention has smooth and flat surface and good salt corrosion resistance.
Example 6
Weighing 20g of dendritic copper powder with the particle size of 20 mu m, ultrasonically washing surface impurities and organic matters with glacial acetic acid for 10min, and carrying out suction filtration for later use. 300mL of hexanol, 20mL of octadecylamine, and 40mL of lithium formate solution were added to a vessel and stirred uniformly. Then the washed copper powder is placed in a container containing the mixed solution and heated and stirred for 24 hours at the temperature of 140 ℃. After natural cooling, the supernatant was decanted off and 200mL of 2.0X 10 -2 Stirring the glutathione with mol/L for 20min, and then carrying out suction filtration and drying to obtain the antioxidant copper powder co-modified by formate and mercaptan. Adding the modified copper powder into a mixed solvent of 5g of polyacrylic resin and 6g of isocyanate, and uniformly stirring for 10min at normal temperature in a natural environment to obtain the conductive slurry with the resistivity of 0.9 multiplied by 10 -6 Ω·m。
Example 7
1g of spherical copper powder having a particle size of 10nm and 1g of flake copper powder having a particle size of 20 μm were weighed and uniformly mixed. 20mL of butanol, 2mL of oleylamine, and 2mL of a potassium formate solution were added to the vessel and stirred uniformly. Then, the copper powder was placed in a container containing the above mixed solution and heated and stirred at 80 ℃ for 1 hour. After natural cooling, the supernatant was decanted off and 20mL of 3.0X 10 -2 And stirring the mercaptoethanol in mol/L for 30s, and then carrying out suction filtration and drying to obtain the antioxidant copper powder co-modified by formate and mercaptan. Modifying the copperAdding 0.6g of epoxy resin and 0.4g of triethanolamine mixed solvent into the powder, and uniformly stirring for 5min in a natural environment at normal temperature to obtain the conductive slurry with the resistivity of 1.2 multiplied by 10 -6 Ω·m。
Example 8
Respectively weighing 1g of spherical copper powder with the particle size of 500nm and 1g of dendritic copper powder with the particle size of 10 mu m, ultrasonically washing surface impurities and organic matters for 10min by glacial acetic acid, and performing suction filtration for later use. 30mL of propylene glycol, 3mL of n-octylamine, and 1mL of magnesium formate solution were added to the vessel and stirred uniformly. Then the two washed copper powders are respectively put into a container containing the mixed solution to be heated and stirred for 3 hours at the temperature of 100 ℃. After natural cooling, the supernatant was decanted off and 20mL of a 4.0X 10 solution was added -2 Stirring the cysteine with mol/L for 10min, and then carrying out suction filtration and drying to obtain two types of formate and mercaptan co-modified antioxidant copper powder with different morphologies. Uniformly mixing the two modified copper powders, adding 0.6g of polyester resin and 1.4g of methyl ethyl ketone peroxide mixed solvent, and uniformly stirring for 6min in a natural environment at normal temperature to obtain conductive slurry with the resistivity of 1.0 multiplied by 10 -6 Ω·m。
Example 9
Weighing 1g of dendritic copper powder with the particle size of 1 mu m and 1g of copper nanowires with the particle size of 15nm and the length of 20 mu m, uniformly mixing, washing surface impurities and organic matters by glacial acetic acid ultrasound for 10min, and performing suction filtration for later use. 30mL of ethylene glycol, 2mL of dodecylamine and 2mL of sodium formate solution are added into a container and stirred uniformly. Then the washed copper powder is placed in a container containing the mixed solution and heated and stirred for 1.5h at the temperature of 120 ℃. After natural cooling, the supernatant was decanted off and 20mL of 5.0X 10 -2 Stirring the dodecyl mercaptan in mol/L for 1min, and then carrying out suction filtration and drying to obtain the antioxidant copper powder co-modified by formate and mercaptan. Adding 0.3g of phenolic resin and 0.7g of triethanolamine mixed solvent into the modified copper powder, and uniformly stirring for 7min in a natural environment at normal temperature to obtain the conductive slurry with the resistivity of 0.9 multiplied by 10 -6 Ω·m。
Example 10
1g of spherical copper powder with the particle size of 5 mu m and 1g of copper nanowire with the particle size of 50nm and the length of 30 mu m are respectively weighed. 30mL of glycerol3mL of oleylamine and 4mL of ammonium formate solution were added to the vessel and stirred well. Then the copper powder and the copper nanowires are respectively placed in a container containing the mixed solution to be heated and stirred for 6 hours at the temperature of 150 ℃. After natural cooling, the supernatant was decanted off and 20mL of 6.0X 10 solution was added -2 Stirring the hexadecanethiol in mol/L for 6min, carrying out suction filtration and drying to obtain formic acid radical and thiol co-modified oxidation-resistant copper powder and copper nanowires, uniformly mixing the two, adding 0.4g of amino resin and 0.7g of ammonium chloride mixed solvent, and uniformly stirring for 8min in a natural environment at normal temperature to obtain conductive slurry with the resistivity of 1.5 multiplied by 10 -6 Ω·m。
Example 11
Weighing 1g of flake copper powder with the particle size of 10 mu m and 1g of dendritic copper powder with the particle size of 500nm, uniformly mixing, washing surface impurities and organic matters by glacial acetic acid ultrasound for 10min, and performing suction filtration for later use. 40mL of glycerol, 1.5mL of n-octylamine and 2mL of calcium formate solution are added to a container and stirred uniformly. Then the washed copper powder is placed in a container containing the mixed solution to be heated and stirred for 12 hours at 180 ℃. And naturally cooling, pouring out the supernatant, adding 20mL of mercaptoethylamine with the concentration of 7.0 multiplied by 10 < -2 > mol/L, stirring for 4min, and performing suction filtration and drying to obtain the formic acid radical and mercaptan co-modified antioxidant copper powder. Adding 0.5g of phenolic resin and 0.5g of triethanolamine mixed solvent into the modified copper powder, and uniformly stirring for 9min in a natural environment at normal temperature to obtain the conductive slurry with the resistivity of 0.9 multiplied by 10 -6 Ω·m。
Example 12
Weighing 1g of dendritic copper powder with the particle size of 20 mu m and 1g of spherical copper powder with the particle size of 50nm, uniformly mixing, washing surface impurities and organic matters by glacial acetic acid ultrasound for 10min, and performing suction filtration for later use. 30mL of hexanol, 3mL of dodecylamine, and 4mL of lithium formate solution were added to a vessel and stirred uniformly. Then the washed copper powder is placed in a container containing the mixed solution and heated and stirred for 24 hours at the temperature of 140 ℃. After natural cooling, the supernatant was decanted off and 20mL of 8.0X 10 -2 Stirring the glutathione with mol/L for 20min, and then carrying out suction filtration and drying to obtain the antioxidant copper powder co-modified by formate and mercaptan. Adding 0.5g of epoxy resin and 0.6g of phenolic aldehyde amine mixed solvent into the modified copper powderUniformly stirring the mixture for 10min in a warm natural environment to obtain the conductive slurry with the resistivity of 1.5 multiplied by 10 -6 Ω·m。
The antioxidant copper material provided by the invention can be used for preparing RFID labels. When the RFID label is prepared, firstly, pattern design of an RFID label antenna is carried out by using simulation software; then, the anti-oxidation copper material provided by the invention is used for printing or etching the tag antenna; and finally, connecting the tag antenna with the IC chip to form a passage, and fixing the IC chip by using the conductive paste to obtain the RFID tag.
In the steps, if the conductive paste provided by the invention is adopted to print on the substrate according to the designed tag antenna, the curing temperature is 80-200 ℃, and the curing time is 20 s-5 min.
According to the invention, a technical means of jointly modifying formate and mercaptan is adopted, and the mercaptan compound is adsorbed on the surface of the copper material modified by formate to form a self-assembled film, so that the corrosion resistance of the copper material is further improved. On the basis that the thermal stability of the copper material is improved by formic acid, the hydrophobic property of the copper material can be obviously improved by introducing the modification of mercaptan, so that a more stable hydrophobic oxidation-resistant layer is formed on the surface of the copper material. In addition, in the scheme, the copper material can achieve a good modification effect only by opening the environment of the container and within a short time. Compared with the copper-containing material before treatment, the copper-containing material treated by the invention has stronger oxidation resistance (including high temperature oxidation resistance), saline-alkali corrosion resistance and higher conductivity, and can be used in the fields of copper-containing materials such as copper-based conductive slurry, transparent conductive film containing copper nanowires, copper foil, copper-based electromagnetic shielding film, copper cable, RFID antenna and the like.
While the foregoing specification illustrates and describes the preferred embodiments of the present invention, it is to be understood that the invention is not limited to the precise forms disclosed herein and is not to be interpreted as excluding the existence of additional embodiments that are also intended to be encompassed by the present invention as modified within the spirit and scope of the invention as described herein. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. An antioxidant copper material is characterized in that the antioxidant copper material is a copper material with the surface modified with formate and mercaptan; the mercaptan is adsorbed on the surface of the copper material modified by the formate;
the preparation method of the antioxidant copper material comprises the following steps:
adding 1-15 mol/L formate solution and solvent into a first container, stirring uniformly to obtain a mixed solution, placing the copper material into the first container containing the mixed solution, reacting at 80-180 ℃ for 0.5-24 h, pouring out supernatant, adding 1.0 multiplied by 10 -4 ～1.0×10 -1 And (3) reacting the mercaptan in mol/L for 0.5-30 min, and then carrying out liquid-solid separation, washing and drying treatment to obtain the antioxidant copper material.
2. The copper antioxidant material of claim 1, wherein the formate salt is at least one of lithium formate, sodium formate, magnesium formate, aluminum tri-formate, potassium formate, ammonium formate, calcium formate, zinc formate, iron formate, copper formate, barium formate, beryllium formate, nickel formate, cobalt formate, manganese formate; the solvent comprises an alcohol solution and at least one of oleylamine, n-octylamine, dodecylamine, n-tridecylamine, dodecyl dimethyl tertiary amine or octadecyl amine; the mercaptan is at least one of methyl mercaptan, ethanethiol, ethanedithiol, dodecanethiol, hexadecanethiol, 1-propanethiol, 1, 3-propanedithiol, mercaptoethanol, cysteine, glutathione and mercaptoethylamine.
3. The copper material of claim 1, wherein the copper material comprises one or more of copper powder, copper nanowires, copper foil, copper wires, copper cables; the particle size of the copper powder is 10 nm-20 mu m.
4. The copper antioxidant material as defined in claim 1, characterized in that the mass ratio of the formate solution to the copper material is 5: 1 to 1: 5, and the mass ratio of the solvent to the copper material is 5: 1 to 100: 1; the mass ratio of the mercaptan to the copper material is 5: 1-50: 1; the mass ratio of the alcohol solution in the solvent to the oleylamine or the n-octylamine or the dodecylamine or the n-tridecylamine or the dodecyl dimethyl tertiary amine or the octadecyl amine is 5: 1-30: 1.
5. An electroconductive paste, characterized in that the electroconductive paste contains 50-80 wt% of the oxidation-resistant copper material of any one of claims 1-4, 9-11 wt% of resin and the balance of curing agent;
the preparation method of the conductive paste comprises the following steps:
(1) Taking the oxidation resistant copper material of any one of claims 1 to 4;
(2) And (2) adding the antioxidant copper material, the resin and the curing agent in the step (1) into a second container, and stirring and dispersing for 5-10 min at room temperature in a common environment to obtain the conductive paste.
6. The conductive paste according to claim 5, wherein the resin is at least one of a phenol resin, an epoxy resin, an amino resin, a polyester resin, a polyurethane, a silicone resin, and a polyacrylic resin; the curing agent is at least one of triethanolamine, phenol aldehyde amine, ammonium chloride, methyl ethyl ketone peroxide, diethylenetriamine and isocyanate.
7. The electroconductive paste according to claim 6, which is prepared by a method comprising:
(1) Weighing 2g of spherical copper powder with the particle size of 5 mu m, washing surface impurities and organic matters by glacial acetic acid ultrasound for 10min, and performing suction filtration for later use; adding 40mL of glycerol, 1mL of dodecyl dimethyl tertiary amine and 2mL of 7mol/L calcium formate solution into a container, uniformly stirring, and then placing the washed copper powder into the container containing the mixed solution, heating at 180 ℃ and stirring for 12 hours; after natural cooling, the supernatant was decanted off and 20mL of 1.0X 10 -2 Stirring the mercaptoethylamine with mol/L for 4min; then carrying out suction filtration and drying to obtain the formate and the mercaptan for co-repairingDecorated anti-oxidant copper powder;
(2) And adding 0.4g of phenolic resin and 0.6g of triethanolamine into the modified antioxidant copper powder, and uniformly stirring for 9min at normal temperature in a natural environment to obtain the conductive slurry.
8. The application of the conductive paste in the RFID label, characterized in that the label antenna of the RFID label is made of the conductive paste of any one of claims 5-7.
9. The application of the conductive paste in the RFID tag, according to claim 8, wherein the conductive paste is cured by transferring the tag antenna to the substrate through screen printing, ink-jet printing or gravure printing, the curing temperature is 80-200 ℃, and the curing time is 20 s-5 min.
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| CN113707362A (en) * | 2021-07-23 | 2021-11-26 | 厦门大学 | High-conductivity copper paste, preparation method, flexible high-conductivity copper film and application thereof |
| CN113764120B (en) * | 2021-08-10 | 2023-01-20 | 厦门大学 | Oxidation-resistant copper film/copper wire and preparation method and application thereof |
| CN113744928B (en) * | 2021-08-10 | 2022-07-22 | 厦门大学 | Antioxidant transparent conductive film and preparation method and application thereof |
| CN114005575B (en) * | 2021-09-26 | 2024-01-12 | 西安隆基乐叶光伏科技有限公司 | Antioxidant conductive copper paste and preparation method and application thereof |
| CN114277376A (en) * | 2021-12-01 | 2022-04-05 | 厦门大学 | Metal oxidation-resistant treatment method |
| CN115287637A (en) * | 2022-06-22 | 2022-11-04 | 南京航空航天大学 | Oxidation-resistant copper material and light or ray induction preparation method thereof |
| CN117107323B (en) * | 2023-10-23 | 2024-01-12 | 武汉大学 | Method and device for improving interface stability of copper-containing part of environment-friendly gas insulation equipment |
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