CN111799012A - Antioxidant copper material and preparation method thereof - Google Patents
Antioxidant copper material and preparation method thereof Download PDFInfo
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- CN111799012A CN111799012A CN202010578213.8A CN202010578213A CN111799012A CN 111799012 A CN111799012 A CN 111799012A CN 202010578213 A CN202010578213 A CN 202010578213A CN 111799012 A CN111799012 A CN 111799012A
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- formate
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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 includes the following steps of preparing Cu nanoparticles, wrapping 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 sintered for 1 hour in an inert atmosphere or vacuum within a temperature range of less than 150 ℃. In order to prevent the copper from being oxidized, the storage of the slurry and the sintering of the circuit need to be 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 copper materials to enhance the oxidation resistance of copper materials. 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, so that 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 antioxidant copper material 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 a surface modified with formate and mercaptan.
The second aspect of the invention provides a preparation method of an antioxidant copper material, which comprises the following steps:
adding a formate solution with the concentration of 1-15 mol/L and a solvent into a first container, uniformly stirring to obtain a mixed solution, then placing a copper material into the first container containing the mixed solution, reacting at the temperature of 80-180 ℃ for 0.5-24 h, pouring out a supernatant, adding a 1.0 x 10 concentration-4～1.0×10-1And (3) reacting the mol/L mercaptan 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 selected from at least one of lithium formate, sodium formate, magnesium formate, aluminum trimethyl carbonate, 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, n-octylamine, dodecylamine, n-tridecylamine, dodecyl dimethyl tertiary amine or octadecyl amine; the mercaptan is preferably at least one of methyl mercaptan, ethyl mercaptan, ethylene glycol mercaptan, dodecyl mercaptan, hexadecyl mercaptan, 1-propyl mercaptan, 1, 3-propanedithiol, mercaptoethanol, cysteine, glutathione and mercaptoethylamine.
Further, the copper material is selected from one of copper powder, copper nanowires, copper foil, 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 oleylamine, n-octylamine, dodecylamine, n-tridecylamine, dodecyl dimethyl tertiary amine or octadecyl amine is 5: 1-30: 1.
The third aspect of the present invention is to provide a conductive paste, which contains 50 to 80 wt% of at least one of the antioxidant copper powder and the copper nanowire, 9 to 11 wt% 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) at least one of the antioxidant copper material of claim 1 or the antioxidant copper powder and copper nanowires prepared by the method for preparing the antioxidant copper material of claim 2;
(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 the 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.
Further, 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 by formate and mercaptan, the copper-containing material subjected to double treatment by formate and mercaptan 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 24h salt spray experiment.
Fig. 4a is an optical photograph of an untreated copper wire after 24h salt spray experiments.
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 provided 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, copper powder (5 μm average particle size) was co-modified with formate and thiolWhen the concentration of mercaptan is less than 1.0X 10-4At 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 the mercaptan exceeds 1.0X 10-1At mol/L, the resistivity of the slurry also starts to increase significantly, because the higher concentration of mercaptan displaces part of the formate adsorption on the surface of the copper material, which leads to the reduction of the thermal stability of the copper powder and the increase of the contact resistance, so that the conductivity of the slurry is greatly reduced in the subsequent curing process. Thus, the formate concentration was 1.0X 10-4～1.0×10-1The 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 made of the copper material modified by the formate or the thiol alone with the resistivity of the conductive paste made of the copper material modified by the formate and the thiol together provided by the invention, it can be known that: 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 10-6～1.5×10-6Omega. m, and the resistivity of the conductive paste made of the copper material modified with only formate is 1.0X 10-5～1.0×10-4Omega. m, resistivity of conductive paste made of copper material modified with thiol only, 1.2X 10-4～3.5×10-4Omega.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 10-1Ω·m、5.4×10-4Ω·m、1.3×10-5Omega.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 10-6Omega.m. Namely, the resistivity of the conductive paste provided by the invention after being placed in the air for 30 days is obviously different from the resistivity of other copper pastes after being placed in the air for 30 days, which shows that the oxidation resistance effect of the conductive paste provided by the invention is obviously improved compared with other copper pastes.
TABLE 3 comparison of resistivities of different conductive pastes before and after 30 days in air
| 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 a particle size of 10nm was weighed. 20mL of butanol, 1.5mL 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 1.0X 10-1The mercaptoethanol in mol/L was stirred for 30 s. 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 10-6Ω·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 10-3The mol/L cysteine was stirred for 10 min. 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 10-6Ω·m。
Example 3
Taking a piece of copper foil with the thickness of 18 mu m, carrying out ultrasonic treatment in glacial acetic acid for 10min, washing surface impurities and organic matters, and drying 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 at 120 ℃ and left to stand for 1.5 hours. After natural cooling, the supernatant was decanted off and 30mL of a 1.0X 10 solution was added-2The mol/L dodecanethiol is allowed to stand for 1 min. Taking out and drying to obtain the antioxidant copper foil co-modified by formate and mercaptan, and immediately testing the resistivity to be 1.8 multiplied by 10-8Omega.m. The resistivity of the film after being exposed in the air for 30 days is still 1.8 multiplied by 10-8Ω·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, it is shown that the contact angle of the copper foil surface after thiol modification alone increases 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 was shown to rise to the highest, 133.5 °. Therefore, the common modification of formate and 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 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, ultrasonic washing surface impurities and organic substances with glacial acetic acid for 10min, and drying for 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 10-4The hexadecanethiol in mol/L is left to stand for 6 min. 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 10-8Omega.m. The resistivity of the film after being exposed in the air for 30 days is still 1.7 multiplied by 10-8Ω·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, washing surface impurities and organic matters by glacial acetic acid ultrasound for 10min, and performing suction filtration for later use. 40mL of glycerol, 1mL of dodecyldimethyl tertiary amine and 2mL of calcium formate solution are added into a container and stirred uniformly. Then the washed copper powder is put into a container containing the mixed solution to be heated and stirred for 12 hours at 180 DEG C. After natural cooling, the supernatant was decanted off and 20mL of 1.0X 10-2The mercaptoethylamine was stirred for 4min at mol/L. 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 10-6Ω·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, washing surface impurities and organic matters by glacial acetic acid ultrasound for 10min, and performing 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 10-2Stirring 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 modified copper powder into a mixed solvent of 5g of polyacrylic resin and 6g of isocyanate, and carrying out normal temperature treatmentUniformly stirring in natural environment for 10min to obtain conductive slurry with resistivity of 0.9 × 10-6Ω·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 10-2And 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. Adding 0.6g of epoxy resin and 0.4g of triethanolamine mixed solvent into the modified copper 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 10-6Ω·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 are added to a container 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-2Stirring 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 the conductive slurry with the resistivity of 1.0 multiplied by 10-6Ω·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 washing the copperThe powder was heated and stirred for 1.5h at 120 ℃ in a vessel containing the above mixed solution. After natural cooling, the supernatant was decanted off and 20mL of 5.0X 10-2Stirring 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 10-6Ω·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 weighed respectively. 30mL of glycerol, 3mL of oleylamine and 4mL of ammonium formate solution were added to the vessel and stirred uniformly. Then the copper powder and the copper nanowires are respectively placed in a container containing the mixed solution and heated and stirred for 6 hours at 150 ℃. After natural cooling, the supernatant was decanted off and 20mL of 6.0X 10 solution was added-2Stirring the hexadecanethiol in mol/L for 6min, performing suction filtration and drying to obtain antioxidant copper powder and copper nanowires which are co-modified by formate and thiol, uniformly mixing the antioxidant copper powder and the copper nanowires, adding 0.4g of amino resin and 0.7g of ammonium chloride mixed solvent, and uniformly stirring the mixture for 8min in a natural environment at normal temperature to obtain the conductive slurry with the resistivity of 1.5 multiplied by 10-6Ω·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 and heated and stirred for 12 hours at 180 ℃. After natural cooling, the supernatant was decanted off and 20mL of a 7.0X 10 solution was added-2And stirring the mercaptoethylamine with the mol/L for 4min, and performing suction filtration and drying to obtain the antioxidant copper powder co-modified by the formate and the mercaptan. 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 10-6Ω·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 10-2Stirring 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 powder, and uniformly stirring for 10min at normal temperature in natural environment to obtain the conductive slurry with the resistivity of 1.5 multiplied by 10-6Ω·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 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 modification process of 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 method 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 films containing copper nanowires, copper foils, copper-based electromagnetic shielding films, copper cables, RFID antennas and the like.
While the foregoing description shows and describes the preferred embodiments of the present invention, it is to be understood that the invention is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as described herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. 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 (10)
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.
2. A preparation method of an antioxidant copper material comprises the following steps:
adding a formate solution with the concentration of 1-15 mol/L and a solvent into a first container, uniformly stirring to obtain a mixed solution, then placing a copper material into the first container containing the mixed solution, reacting at the temperature of 80-180 ℃ for 0.5-24 h, pouring out a supernatant, adding a 1.0 x 10 concentration-4～1.0×10-1And (3) reacting the mol/L mercaptan for 0.5-30 min, and then carrying out liquid-solid separation, washing and drying treatment to obtain the antioxidant copper material.
3. The process for producing copper materials resistant to oxidation according to claim 2, wherein the formate is at least one selected from the group consisting of lithium formate, sodium formate, magnesium formate, aluminum tricarbomate, 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 at least one of oleylamine, n-octylamine, dodecylamine, n-tridecylamine, dodecyl dimethyl tertiary amine or octadecyl amine; the mercaptan is preferably at least one of methyl mercaptan, ethyl mercaptan, ethylene glycol mercaptan, dodecyl mercaptan, hexadecyl mercaptan, 1-propyl mercaptan, 1, 3-propanedithiol, mercaptoethanol, cysteine, glutathione and mercaptoethylamine.
4. The method for preparing copper materials with oxidation resistance according to claim 2, wherein the copper materials include copper powder, copper nanowires, copper foil, copper wires, copper cables, but not limited thereto; the particle size of the copper powder is 10 nm-20 mu m.
5. The method for preparing an antioxidant copper material as defined in claim 2, wherein 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 oleylamine, n-octylamine, dodecylamine, n-tridecylamine, dodecyl dimethyl tertiary amine or octadecyl amine is 5: 1-30: 1.
6. A conductive paste comprising the copper material according to claim 1 or at least one of the copper powder and the copper nanowire obtained by the method for preparing the copper material according to claim 2, wherein the conductive paste comprises 50-80 wt% of the copper material, 9-11 wt% of resin and the balance of a curing agent.
7. The conductive paste according to claim 6, 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.
8. A method of preparing a conductive paste, comprising the steps of:
(1) at least one of the antioxidant copper material of claim 1 or the antioxidant copper powder and copper nanowires prepared by the method for preparing the antioxidant copper material of claim 2;
(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.
9. The application of the conductive paste in the RFID tag is characterized in that the tag antenna of the RFID tag is prepared from the conductive paste prepared by the conductive paste according to the claim 6 or the method for preparing the conductive paste according to the claim 8.
10. The application of the conductive paste in the RFID tag, according to claim 9, wherein the conductive paste is used for transferring the tag antenna to the substrate for curing 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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