CN110029330B - Copper-zinc alloy composite material and preparation method thereof - Google Patents

Copper-zinc alloy composite material and preparation method thereof Download PDF

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CN110029330B
CN110029330B CN201810031498.6A CN201810031498A CN110029330B CN 110029330 B CN110029330 B CN 110029330B CN 201810031498 A CN201810031498 A CN 201810031498A CN 110029330 B CN110029330 B CN 110029330B
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copper
zinc
graphite
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zinc alloy
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CN110029330A (en
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李周
龚深
肖柱
王洋
吴迪
肖韬
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by electroless plating
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • C23C18/1692—Heat-treatment
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/52—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/101—Sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

Abstract

The invention discloses a copper-zinc alloy composite material, which consists of graphite or foam carbon and a copper-zinc alloy layer on the surface layer of the graphite or foam carbon, wherein the copper-zinc alloy layer is obtained by alloying a copper coating and a zinc coating, and the copper-zinc alloy layer consists of the following components in percentage by weight: 40-80% of copper and 20-60% of zinc. The copper-zinc alloy composite material adopts graphite or foam carbon as a substrate, has a large specific surface area and strong adsorbability, can remove chlorine, ammonia chloride and other organic substances, and generates a synergistic effect between the copper-zinc alloy layer and the graphite or the foam carbon; according to the invention, the copper-zinc alloy layers with different crystal grain sizes can be obtained by regulating and controlling the process parameters, the purity is high, the coating is uniform, the thickness is controllable, the interface combination of the obtained copper-zinc alloy layer and graphite or foam carbon is good, the contact angle between the surface of the alloy layer and water and glycerol is small, and the wettability is good; the method has the advantages of simple process, low cost and low equipment requirement, and can be suitable for large-scale production.

Description

Copper-zinc alloy composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a copper-zinc alloy composite material and a preparation method thereof.
Background
The copper-zinc alloy (KDF) is a novel water filtering medium invented by Don Heskett doctor of American scientist in 1984, the water purification principle of the KDF is that water treatment is carried out through electrochemical oxidation-reduction, so that bacterial breeding can be inhibited, pollutants such as heavy metal, chlorine, hydrogen sulfide and the like in water can be removed, the service life of the KDF is long, the KDF is widely popularized in the field of water treatment, but the KDF is not strong in adsorption capacity and poor in single use effect, and is mainly used by being directly mixed with active carbon particles, so that particles are easy to block equipment pipelines, a large amount of filtering materials are wasted, and the maintenance cost is increased.
At present, the electric arc spraying technology is mainly adopted for preparing the copper-zinc alloy layer, the purity of the prepared copper-zinc alloy layer is low, the coating is uneven, particularly, the refining level of copper cannot meet the process requirement, and in the actual use process, copper can react with oxidizing substances in water to generate copper compounds and complexes, so that the excessive copper ions in the water are generated, and the potential risk of heavy metal poisoning exists.
Disclosure of Invention
The invention aims to provide a copper-zinc alloy composite material which is not easy to block an equipment pipeline, has high purity, uniform plating and low cost and a preparation method thereof.
The invention relates to a copper-zinc alloy composite material, which consists of matrix graphite or foam carbon and a copper-zinc alloy layer on the surface layer of the matrix graphite or foam carbon, wherein the copper-zinc alloy layer is obtained by alloying a copper coating and a zinc coating, and the copper-zinc alloy layer consists of the following components in percentage by weight: 40-80% of copper and 20-60% of zinc.
Preferably, the thickness of the copper-zinc alloy layer is 2-40 μm; more preferably, the thickness of the copper-zinc alloy layer is 5 to 20 μm.
The invention also provides a preparation method of the copper-zinc alloy composite material, which comprises the following steps:
(1) acid treatment: putting graphite or carbon foam into a mixed solution of concentrated sulfuric acid and concentrated nitric acid for ultrasonic treatment, and cleaning to obtain acid-treated graphite or carbon foam;
(2) sensitization treatment: dissolving stannous chloride in concentrated hydrochloric acid, diluting to obtain a sensitizing solution, adding the acid-treated graphite or carbon foam obtained in the step (1) into the sensitizing solution for ultrasonic treatment, and cleaning to obtain sensitized graphite or carbon foam;
(3) activation treatment: dissolving palladium chloride in concentrated hydrochloric acid, diluting to obtain an activation solution, adding the sensitized graphite or carbon foam obtained in the step (2) into the activation solution for ultrasonic treatment, and cleaning to obtain the activated graphite or carbon foam;
(4) copper plating on the surface of graphite or foam carbon: adding the activated graphite or the activated carbon obtained in the step (3) into a copper plating solution, adding bipyridine serving as a stabilizer, heating the plating solution, adding glyoxylic acid serving as a reducing agent, adjusting the pH, reacting for a certain time, taking out the graphite or the carbon foam, and cleaning to obtain copper-plated graphite or carbon foam;
(5) and (3) plating zinc on the surface of graphite or foam carbon: adding the copper-plated graphite or the carbon foam obtained in the step (4) into a zinc plating solution, heating to boil, reacting for a certain time, taking out the graphite or the carbon foam, and cleaning to obtain the copper-zinc-plated graphite or the carbon foam;
(6) alloying treatment of the copper-zinc coating: and (4) freeze-drying the copper-zinc plated graphite or the foam carbon obtained in the step (5), then heating to 240-280 ℃ to alloy the copper-zinc plating layer, then carrying out quenching treatment, and cleaning and drying to obtain the copper-zinc alloy composite material.
The volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the step (1) is (2-4): 1.
in the step (2), the mass-to-volume ratio of the stannous chloride to the concentrated hydrochloric acid is 1: 1g/ml, wherein the mass concentration of the concentrated hydrochloric acid is 36-38%, and the raw materials are calculated according to the volume part, 2-3 parts of concentrated hydrochloric acid solution of stannous chloride are taken, and water is added to dilute the solution to 100 parts, so that the sensitizing solution is obtained.
In the step (3), the mass-to-volume ratio of the palladium chloride to the concentrated hydrochloric acid is 1: 20g/ml, wherein the mass concentration of the concentrated hydrochloric acid is 36-38%, and the raw materials are calculated according to parts by volume, 1-3 parts of concentrated hydrochloric acid solution of palladium chloride are added with water to be diluted to 100 parts, so as to obtain the activation solution.
The copper plating solution in the step (4) is obtained by the following steps: weighing 25-35 parts of CuSO by weight of raw materials4·5H2O, 70-90 parts of EDTANa225-30 parts of NaKC4H4O6·4H2And dissolving 30-35 parts of KOH in 400-450 parts of water, and uniformly stirring to obtain the copper plating solution. The EDTANA2And NaKC4H4O6As a complexing agent, the copper ion complexing agent can prevent the copper ion from generating precipitation after being complexed with the copper ion.
In the step (4), 20-30 parts by volume of copper plating solution is taken as a raw material, 10-15 parts of 2, 2-bipyridyl solution is added, the concentration of the bipyridyl solution is (0.1-0.3 g)/100ml, water is added to dilute the bipyridyl solution to 80-100 parts, activated graphite or carbon foam obtained in the step (3) is added, the plating solution is heated to 55-65 ℃ by water bath, 1-2 parts of glyoxylic acid are added, and 10mol/L KOH is adopted to adjust the pH of the reaction solution to 11.5-13. The 2, 2-bipyridine is used as a stabilizer in the copper plating reaction, can stabilize the plating solution, and can adjust the size of copper-plated grains to refine the grains.
The zinc plating solution in the step (5) is obtained by the following steps: preparing a zinc chloride solution with the concentration of 0.6-0.8 g/ml, taking 400 parts of the zinc chloride solution by volume of raw materials, adding 30-35 parts of 2, 2-bipyridyl solution, adding zinc powder with the particle size of 100-300 mu m, and stirring to obtain a silver gray turbid solution, namely a zinc plating solution.
In the step (6), the copper-zinc plated graphite or carbon foam is freeze-dried for more than 5 hours, then placed into high-temperature silicone oil, heated to 240-280 ℃, reacted for 2-3 hours, so that the copper-zinc plating layer is alloyed, after sufficient alloying, a sample is quenched into ice water, residual silicone oil on the surface of the sample is removed by using a detergent in an ultrasonic cleaning machine, and then the sample is washed by using a large amount of deionized water and dried to obtain the surface copper-zinc alloy composite material.
Compared with the prior art, the invention has the beneficial technical effects that:
(1) the copper-zinc alloy composite material adopts graphite or foam carbon as a substrate, has larger specific surface area and strong adsorbability, can remove chlorine, ammonia chloride and other organic substances, generates synergistic effect between a copper-zinc alloy layer and the graphite or the foam carbon, can inhibit bacterial breeding by the copper-zinc alloy layer through the principle of electrochemical oxidation-reduction, removes pollutants such as heavy metal, hydrogen sulfide and the like in water, improves the water purification capacity, has long service life, is not easy to block equipment pipelines, and is an ideal water purification filter layer material.
(2) The invention can obtain the copper-zinc alloy layer with different crystal grain sizes by regulating and controlling the process parameters, the purity is high, the plating layer is uniform, the thickness is controllable, the interface combination of the obtained copper-zinc alloy layer and graphite or foam carbon is good, the contact angle between the surface of the alloy layer and water and glycerol is small, and the wettability is good.
(3) The method has the advantages of simple process, low cost and low equipment requirement, and can be suitable for large-scale production.
Drawings
FIG. 1 is a scanning electron microscope image of the appearance of a sample after copper plating according to example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of the appearance of a galvanized sample in example 1 of the present invention.
FIG. 3 is a scanning electron microscope image and an appearance of the alloyed sample in example 1 of the present invention.
FIG. 4 is a photograph of a water droplet on the surface of a Cu-Zn alloy layer according to example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without any creative work based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1
The invention relates to a preparation method of a copper-zinc alloy composite material, which comprises the following steps:
(1) acid treatment: the method comprises the following steps of (1) taking a high-purity graphite rod as a substrate, putting the graphite rod with the size of 50mm in length, 5mm in width and 5mm in height into a mixed solution (volume ratio is 3: 1) of concentrated sulfuric acid and concentrated nitric acid for ultrasonic treatment for 10min, and cleaning the graphite rod with a large amount of deionized water to obtain an acid-treated graphite rod;
(2) sensitization treatment: weighing 2.5g of stannous chloride, dissolving the stannous chloride in 2.5ml of concentrated hydrochloric acid (the mass concentration is 36%), adding water to dilute the stannous chloride to 100ml to obtain sensitizing solution, adding the graphite rod subjected to acid treatment obtained in the step (1) into the sensitizing solution, carrying out ultrasonic treatment for 10min, and cleaning the graphite rod with a large amount of deionized water to obtain a sensitized graphite rod;
(3) activation treatment: weighing 0.25g of palladium chloride, dissolving in 5ml of concentrated hydrochloric acid (the mass concentration is 36%), adding water for diluting to 250ml to obtain an activation solution, adding the sensitized graphite rod obtained in the step (2) into the activation solution for ultrasonic treatment for 10min, and cleaning with a large amount of deionized water to obtain the activated graphite rod;
(4) copper plating on the surface of the graphite rod: adding the graphite rod subjected to the activation treatment in the step (3) into 25ml of copper plating solution, adding 12ml of 2, 2-bipyridine serving as a stabilizer, wherein the concentration of the bipyridine solution is 0.2g/100ml, then adding water to dilute the bipyridine solution to 90ml, heating the plating solution to 60 ℃ in a water bath, adding 1.5ml of glyoxylic acid serving as a reducing agent, adjusting the pH to 12 by using 10mol/L KOH concentrated solution, timing after the surface of the graphite rod is red, taking out the graphite rod after 8min, cleaning the graphite rod by using a large amount of deionized water to obtain a copper-plated graphite rod, wherein the appearance and the appearance of the copper-plated sample and a scanning electron microscope picture are shown in a figure 1;
preparing the copper plating solution: preparing 500ml of copper plating solution by using a volumetric flask, and sequentially adding the following medicines: 30g of CuSO4·5H2O；80g EDTANa2；28g NaKC4H4O6·4H2O; 34g KOH and finally water to 500 ml;
(5) and (3) plating zinc on the surface of the graphite rod: adding the copper-plated graphite rod obtained in the step (4) into 150ml of zinc plating solution, heating to boil, reacting for 8min, taking out the graphite rod, cleaning with a large amount of deionized water to obtain the copper-zinc plated graphite rod, wherein the appearance and the scanning electron microscope picture of the galvanized sample are shown in figure 2;
preparing the zinc plating solution: weighing 280g ZnCl2Adding water to 400ml in a beaker, stirring and dissolvingAdding 32ml of 2, 2-bipyridine as a stabilizer, adding 2g of zinc powder (the particle size is 100-300 um), and uniformly stirring to obtain a silver gray turbid solution;
(6) alloying treatment of the copper-zinc coating: and (3) freeze-drying the copper-zinc plated graphite rod obtained in the step (5) for 6h, heating the copper-zinc plated graphite rod in a silicon oil bath to 240 ℃ to alloy a copper-zinc plating layer for 2h, quenching the sample into ice water, removing residual silicon oil on the surface of the sample by using a detergent in an ultrasonic cleaning machine, washing the sample by using a large amount of deionized water, and drying to obtain the graphite rod with the copper-zinc alloy layer plated on the surface, wherein the appearance and the scanning electron microscope picture of the alloyed sample are shown in figure 3, and the structural parameters and the performance of the copper-zinc alloy layer plated in the embodiment are shown in table 1.
As can be seen from fig. 1-3, the copper plating layer, the zinc plating layer and the copper-zinc alloy layer of the present embodiment are uniform and dense, and the coating is complete, the shape of water drops on the surface of the copper-zinc alloy layer is shown in fig. 4, and the wettability of the copper-zinc alloy layer and water is good. As can be seen from table 1, the composition of the copper-zinc alloy layer is: 50 wt% of copper and 50 wt% of zinc; the thickness of the alloy layer is 10 μm, the grain size is smaller and is 225 nm; the adhesive tape experiment result shows that the bonding force between the alloy layer and the substrate is strong, and the alloy layer is not easy to fall off in the using process; in addition, the contact angles of the alloy layer with the ionized water and the glycerol are smaller, namely 61.22 degrees and 86.68 degrees respectively, which shows that the alloy layer can have an affinity interface with most of the water solution of the treatment object, and the method is favorable for improving the sewage treatment capability of the alloy layer.
TABLE 1 structural parameters and properties of the Cu-Zn alloy layer plated on the surface of the high purity graphite rod of this example
Figure BDA0001546635380000051
Example 2
The invention relates to a preparation method of a copper-zinc alloy composite material, which comprises the following steps:
(1) acid treatment: the method comprises the following steps of (1) taking a high-purity graphite rod as a substrate, wherein the size of the graphite rod is 50mm in length, 5mm in width and 5mm in height, putting the graphite rod into a mixed solution (volume ratio is 2: 1) of concentrated sulfuric acid and concentrated nitric acid for ultrasonic treatment for 10min, and cleaning the graphite rod with a large amount of deionized water to obtain the graphite rod after acid treatment;
(2) sensitization treatment: weighing 2.5g of stannous chloride, dissolving the stannous chloride in 2.5ml of concentrated hydrochloric acid (the mass concentration is 36%), adding water to dilute the stannous chloride to 100ml to obtain sensitizing solution, adding the graphite rod subjected to acid treatment obtained in the step (1) into the sensitizing solution, carrying out ultrasonic treatment for 10min, and cleaning the graphite rod with a large amount of deionized water to obtain a sensitized graphite rod;
(3) activation treatment: weighing 0.25g of palladium chloride, dissolving in 5ml of concentrated hydrochloric acid (the mass concentration is 36%), adding water for diluting to 250ml to obtain an activation solution, adding the sensitized graphite rod obtained in the step (2) into the activation solution for ultrasonic treatment for 10min, and cleaning with a large amount of deionized water to obtain the activated graphite rod;
(4) copper plating on the surface of the graphite rod: adding the activated graphite rod obtained in the step (3) into 25ml of copper plating solution (same as the example 1), adding 12ml of 2, 2-bipyridine serving as a stabilizer, then adding water to dilute the solution to 100ml, heating the solution to 60 ℃ in a water bath, adding 1.5ml of glyoxylic acid serving as a reducing agent, adjusting the pH to 12 by using 10mol/L KOH concentrated solution, starting timing after the surface of the graphite rod is red, taking out the graphite rod after 4min, and cleaning the graphite rod by using a large amount of deionized water to obtain a copper-plated graphite rod;
(5) and (3) plating zinc on the surface of the graphite rod: adding the copper-plated graphite rod obtained in the step (4) into 150ml of zinc plating solution (same as the example 1), heating to boil, reacting for 8min, taking out the graphite rod, and cleaning with a large amount of deionized water to obtain the copper-zinc plated graphite rod;
(6) alloying treatment of the copper-zinc coating: and (3) freeze-drying the graphite rod coated with the copper-zinc alloy layer obtained in the step (5) for 6h, heating the graphite rod to 250 ℃ in a silicon oil bath to alloy the copper-zinc coating for 2h, quenching the sample into ice water, removing residual silicon oil on the surface of the sample by using a detergent in an ultrasonic cleaning machine, washing the sample by using a large amount of deionized water, and drying to obtain the graphite rod coated with the copper-zinc alloy layer on the surface, wherein the structural parameters and the performances of the copper-zinc alloy layer coated in the embodiment are shown in Table 2.
Table 2 structural parameters and properties of the copper-zinc alloy layer plated on the surface of the high purity graphite rod according to this embodiment
Figure BDA0001546635380000061
As can be seen from table 2, the composition of the copper-zinc alloy layer is: 40 wt% of copper and 60 wt% of zinc; the thickness of the alloy layer is 8 μm, the grain size is smaller and is 208 nm; the adhesive tape experiment result shows that the bonding force between the alloy layer and the substrate is strong, and the alloy layer is not easy to fall off in the using process; in addition, the contact angles of the alloy layer with the ionized water and the glycerol are 72.33 degrees and 88.84 degrees respectively, which shows that the alloy layer can have an affinity interface with most of the water solution of the treatment object, and the affinity interface is favorable for improving the sewage treatment capability of the alloy layer.
Example 3
The invention relates to a preparation method of a copper-zinc alloy composite material, which comprises the following steps:
(1) acid treatment: the method comprises the following steps of (1) taking a high-purity graphite rod as a substrate, putting the graphite rod with the size of 50mm in length, 5mm in width and 5mm in height into a mixed solution (volume ratio is 3: 1) of concentrated sulfuric acid and concentrated nitric acid for ultrasonic treatment for 10min, and cleaning the graphite rod with a large amount of deionized water to obtain an acid-treated graphite rod;
(2) sensitization treatment: weighing 2.5g of stannous chloride, dissolving the stannous chloride in 2.5ml of concentrated hydrochloric acid (the mass concentration is 36%), adding water to dilute the stannous chloride to 100ml to obtain sensitizing solution, adding the graphite rod subjected to acid treatment obtained in the step (1) into the sensitizing solution, carrying out ultrasonic treatment for 10min, and cleaning the graphite rod with a large amount of deionized water to obtain a sensitized graphite rod;
(3) activation treatment: weighing 0.25g of palladium chloride, dissolving in 5ml of concentrated hydrochloric acid (the mass concentration is 36%), adding water for diluting to 250ml to obtain an activation solution, adding the sensitized graphite rod obtained in the step (2) into the activation solution for ultrasonic treatment for 10min, and cleaning with a large amount of deionized water to obtain the activated graphite rod;
(4) copper plating on the surface of the graphite rod: adding the activated graphite rod obtained in the step (3) into 25ml of copper plating solution (same as the example 1), adding 12ml of 2, 2-bipyridine serving as a stabilizer, then adding water to dilute the solution to 90ml, heating the solution to 60 ℃ in a water bath, adding 1.5ml of glyoxylic acid serving as a reducing agent, adjusting the pH to 12 by using 10mol/L KOH concentrated solution, timing after the surface of the graphite rod is red, taking out the graphite rod after 8min, and cleaning the graphite rod by using a large amount of deionized water to obtain a copper-plated graphite rod;
(5) and (3) plating zinc on the surface of the graphite rod: adding the copper-plated graphite rod obtained in the step (4) into 150ml of zinc plating solution (same as the example 1), heating to boil, reacting for 1min, taking out the graphite rod, and cleaning with a large amount of deionized water to obtain the copper-zinc plated graphite rod;
(6) alloying treatment of the copper-zinc coating: and (3) freeze-drying the graphite rod coated with the copper-zinc alloy layer obtained in the step (5) for 6h, heating the graphite rod in a silicon oil bath to 240 ℃ to alloy the copper-zinc coating for 2h, quenching the sample into ice water, removing residual silicon oil on the surface of the sample by using a detergent in an ultrasonic cleaning machine, washing the sample by using a large amount of deionized water, and drying to obtain the graphite rod coated with the copper-zinc alloy layer on the surface, wherein the structural parameters and the performances of the copper-zinc alloy layer coated in the embodiment are shown in Table 3.
TABLE 3 structural parameters and properties of the Cu-Zn alloy layer plated on the surface of the high purity graphite rod of this example
Figure BDA0001546635380000071
As can be seen from table 3, the composition of the copper-zinc alloy layer is: 80 wt% of copper and 20 wt% of zinc; the thickness of the alloy layer is 5 μm, the grain size is smaller and is 225 nm; the adhesive tape experiment result shows that the bonding force between the alloy layer and the substrate is strong, and the alloy layer is not easy to fall off in the using process; in addition, the contact angles of the alloy layer with the ionized water and the glycerol are 59.37 degrees and 83.27 degrees respectively, which shows that the alloy layer can have an affinity interface with most of the water solution of the treatment object, and the method is favorable for improving the sewage treatment capability of the alloy layer.
Example 4
The invention relates to a preparation method of a copper-zinc alloy composite material, which comprises the following steps:
(1) acid treatment: the method comprises the following steps of (1) taking a high-purity graphite plate as a substrate, wherein the size of the graphite plate is 50mm in length, 50mm in width and 5mm in thickness, putting a graphite rod into a mixed solution (volume ratio is 3: 1) of concentrated sulfuric acid and concentrated nitric acid for ultrasonic treatment for 10min, and cleaning the graphite rod with a large amount of deionized water to obtain the graphite rod after acid treatment;
(2) sensitization treatment: weighing 2.5g of stannous chloride, dissolving the stannous chloride in 2.5ml of concentrated hydrochloric acid (the mass concentration is 36%), adding water to dilute the stannous chloride to 100ml to obtain sensitizing solution, adding the graphite plate subjected to acid treatment obtained in the step (1) into the sensitizing solution, carrying out ultrasonic treatment for 10min, and cleaning the graphite plate by using a large amount of deionized water to obtain a sensitized graphite rod;
(3) activation treatment: weighing 0.25g of palladium chloride, dissolving in 5ml of concentrated hydrochloric acid (the mass concentration is 36%), adding water for diluting to 250ml to obtain an activation solution, adding the sensitized graphite plate obtained in the step (2) into the activation solution for ultrasonic treatment for 10min, and cleaning with a large amount of deionized water to obtain an activated graphite plate;
(4) copper plating on the surface of the graphite plate: adding the activated graphite plate obtained in the step (3) into 25ml of copper plating solution (same as the example 1), adding 6ml of 2, 2-bipyridine serving as a stabilizer, then adding water to dilute the solution to 90ml, heating the solution to 60 ℃ in a water bath, adding 1.5ml of glyoxylic acid serving as a reducing agent, adjusting the pH to 12.5 by using 10mol/L KOH concentrated solution, timing after the surface of the graphite plate is red, taking out the graphite plate after 8min, and cleaning the graphite plate by using a large amount of deionized water to obtain a copper-plated graphite plate;
(5) plating zinc on the surface of the graphite plate: adding the copper-plated graphite plate obtained in the step (4) into 150ml of zinc plating solution (same as the example 1), heating to boil, reacting for 8min, taking out the graphite plate, and cleaning with a large amount of deionized water to obtain the copper-zinc plated graphite plate;
(6) alloying treatment of the copper-zinc coating: and (3) freeze-drying the graphite plate coated with the copper-zinc alloy layer obtained in the step (5) for 6h, heating the graphite plate to 260 ℃ in a silicon oil bath to alloy the copper-zinc alloy layer for 2h, quenching the sample into ice water, removing residual silicon oil on the surface of the sample by using a detergent in an ultrasonic cleaning machine, washing the sample by using a large amount of deionized water, and drying to obtain the graphite plate coated with the copper-zinc alloy layer on the surface.
TABLE 4 structural parameters and properties of the Cu-Zn alloy layer plated on the surface of the high purity graphite plate in this example
Figure BDA0001546635380000081
As can be seen from table 4, the composition of the copper-zinc alloy layer is: 50 wt% of copper and 50 wt% of zinc; the thickness of the alloy layer is 10 μm, and the grain size is 413 nm; the adhesive tape experiment result shows that the bonding force between the alloy layer and the substrate is strong, and the alloy layer is not easy to fall off in the using process; in addition, the contact angles of the alloy layer with the ionized water and the glycerol are 55.35 degrees and 85.20 degrees respectively, which shows that the alloy layer can have an affinity interface with most of the water solution of the treatment object, and the affinity interface is favorable for improving the sewage treatment capability of the alloy layer.
Example 5
The invention relates to a preparation method of a copper-zinc alloy composite material, which comprises the following steps:
(1) acid treatment: adopting foam carbon as a substrate, wherein the size of the foam carbon is 50mm in length, 50mm in width and 5mm in height, putting the foam carbon into a mixed solution (the volume ratio is 2: 1) of concentrated sulfuric acid and concentrated nitric acid for ultrasonic treatment for 10min, and cleaning the foam carbon by using a large amount of deionized water to obtain acid-treated foam carbon;
(2) sensitization treatment: weighing 2.5g of stannous chloride, dissolving the stannous chloride in 2.5ml of concentrated hydrochloric acid (the mass concentration is 36%), adding water to dilute the stannous chloride to 100ml of concentrated hydrochloric acid to obtain sensitizing solution, adding the acid-treated carbon foam obtained in the step (1) into the sensitizing solution, carrying out ultrasonic treatment for 10min, and cleaning the carbon foam with a large amount of deionized water to obtain sensitized carbon foam;
(3) activation treatment: weighing 0.25g of palladium chloride, dissolving in 5ml of concentrated hydrochloric acid (the mass concentration is 36%), adding water for diluting to 250ml to obtain an activation solution, adding the sensitized carbon foam obtained in the step (2) into the activation solution for ultrasonic treatment for 10min, and cleaning with a large amount of deionized water to obtain the activated carbon foam;
(4) copper plating on the surface of the foam carbon: adding the activated carbon foam obtained in the step (3) into 25ml of copper plating solution (same as in example 1), adding 12ml of 2, 2-bipyridine as a stabilizer, then adding water to dilute the solution to 90ml, heating the plating solution to 60 ℃ in a water bath, adding 1.5ml of glyoxylic acid as a reducing agent, adjusting the pH to 12.5 by using 10mol/L KOH concentrated solution, timing after the surface of the carbon foam is red, taking out the carbon foam after 18min, and cleaning the carbon foam by using a large amount of deionized water to obtain copper-plated carbon foam;
(5) and (3) surface galvanizing of the foam carbon: adding the copper-plated carbon foam obtained in the step (4) into 150ml of zinc plating solution, heating to boil, reacting for 12min, taking out the carbon foam, and cleaning with a large amount of deionized water to obtain copper-zinc plated carbon foam;
preparing the zinc plating solution: weighing 280g ZnCl2Adding water to 400ml in a beaker, stirring for dissolving, adding 32ml of 2, 2-bipyridine serving as a stabilizer, adding 4g of zinc powder (the particle size is 100-300 um), and uniformly stirring to obtain a silver gray turbid solution;
(6) alloying treatment of the copper-zinc coating: and (3) freeze-drying the copper-zinc plated foam carbon obtained in the step (5) for 6h, heating the copper-zinc plated foam carbon in a silicon oil bath to 250 ℃ to alloy a copper-zinc plating layer for 2h, quenching the sample into ice water, removing residual silicon oil on the surface of the sample by using a detergent in an ultrasonic cleaning machine, washing the sample by using a large amount of deionized water, and drying to obtain the copper-zinc alloy layer plated foam carbon, wherein the structural parameters and the performances of the copper-zinc alloy layer plated in the embodiment are shown in table 5.
TABLE 5 structural parameters and Properties of the copper-zinc alloy layer plated on the surface of the foam carbon in this example
Figure BDA0001546635380000101
As can be seen from table 5, the composition of the copper-zinc alloy layer is: 50 wt% of copper and 50 wt% of zinc; the thickness of the alloy layer is 20 μm, and the grain size is 235 nm; the adhesive tape experiment result shows that the bonding force between the alloy layer and the substrate foam carbon is strong, and the alloy layer is not easy to fall off in the using process; in addition, the contact angles of the alloy layer with the ionized water and the glycerol are 64.18 degrees and 86.42 degrees respectively, which shows that the alloy layer can have an affinity interface with most of the water solution of the treatment object, and the affinity interface is favorable for improving the sewage treatment capability of the alloy layer. The invention adopts graphite or foam carbon as a substrate, then carries out chemical copper plating, chemical zinc plating and alloying treatment on the substrate, and plates a copper-zinc alloy layer on the surface of the graphite or foam carbon, so that the graphite or foam carbon has high purity, uniform plating layer, controllable thickness and low cost, and can be used as an ideal water purification material.

Claims (9)

1. The copper-zinc alloy composite material is characterized by comprising matrix graphite or foam carbon and a copper-zinc alloy layer on the surface layer of the matrix graphite or foam carbon, wherein the copper-zinc alloy layer is obtained by alloying a copper coating and a zinc coating, and the copper-zinc alloy layer comprises the following components in percentage by weight: 40-80% of copper and 20-60% of zinc;
the preparation method of the copper-zinc alloy composite material comprises the following steps:
(1) acid treatment: putting graphite or carbon foam into a mixed solution of concentrated sulfuric acid and concentrated nitric acid for ultrasonic treatment, and cleaning to obtain acid-treated graphite or carbon foam;
(2) sensitization treatment: dissolving stannous chloride in concentrated hydrochloric acid, diluting to obtain a sensitizing solution, adding the acid-treated graphite or carbon foam obtained in the step (1) into the sensitizing solution for ultrasonic treatment, and cleaning to obtain sensitized graphite or carbon foam;
(3) activation treatment: dissolving palladium chloride in concentrated hydrochloric acid, diluting to obtain an activation solution, adding the sensitized graphite or carbon foam obtained in the step (2) into the activation solution for ultrasonic treatment, and cleaning to obtain the activated graphite or carbon foam;
(4) copper plating on the surface of graphite or foam carbon: adding the activated graphite or the activated carbon obtained in the step (3) into a copper plating solution, adding bipyridine serving as a stabilizer, heating the plating solution, adding glyoxylic acid serving as a reducing agent, adjusting the pH, reacting for a certain time, taking out the graphite or the carbon foam, and cleaning to obtain copper-plated graphite or carbon foam;
(5) and (3) plating zinc on the surface of graphite or foam carbon: adding the copper-plated graphite or the carbon foam obtained in the step (4) into a zinc plating solution, heating to boil, reacting for a certain time, taking out the graphite or the carbon foam, and cleaning to obtain the copper-zinc-plated graphite or the carbon foam;
(6) alloying treatment of the copper-zinc coating: and (4) freeze-drying the copper-zinc plated graphite or the foam carbon obtained in the step (5), then heating to 240-280 ℃ to alloy the copper-zinc plating layer, then carrying out quenching treatment, and cleaning and drying to obtain the copper-zinc alloy composite material.
2. The copper-zinc alloy composite material according to claim 1, wherein the thickness of the copper-zinc alloy layer is 2 to 40 μm.
3. The copper-zinc alloy composite material according to claim 1, wherein the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the step (1) is (2-4): 1.
4. the copper-zinc alloy composite material according to claim 1, wherein the mass-to-volume ratio of stannous chloride to concentrated hydrochloric acid in the step (2) is 1: 1g/ml, wherein the mass concentration of the concentrated hydrochloric acid is 36-38%, and the raw materials are calculated according to the volume part, 2-3 parts of concentrated hydrochloric acid solution of stannous chloride are taken, and water is added to dilute the solution to 100 parts, so that the sensitizing solution is obtained.
5. The copper-zinc alloy composite material according to claim 1, wherein the mass-to-volume ratio of the palladium chloride to the concentrated hydrochloric acid in the step (3) is 1: 20g/ml, wherein the mass concentration of the concentrated hydrochloric acid is 36-38%, and the raw materials are calculated according to parts by volume, 1-3 parts of concentrated hydrochloric acid solution of palladium chloride are added with water to be diluted to 100 parts, so as to obtain the activation solution.
6. The copper-zinc alloy composite material according to claim 1, wherein the copper plating solution in the step (4) is obtained by: weighing 25-35 parts of CuSO by weight of raw materials4·5H2O, 70-90 parts of EDTANa225-30 parts of NaKC4H4O6·4H2And dissolving 30-35 parts of KOH in 400-450 parts of water, and uniformly stirring to obtain the copper plating solution.
7. The copper-zinc alloy composite material according to claim 1, wherein in the step (4), 20 to 30 parts by volume of the copper plating solution is taken as a raw material, 10 to 15 parts by volume of 2, 2-bipyridine solution is added, the concentration of the bipyridine solution is (0.1 to 0.3g)/100ml, then water is added to dilute the solution to 80 to 100 parts, the activated graphite or the activated carbon foam obtained in the step (3) is added, the plating solution is heated to 55 to 65 ℃ by using a water bath, 1 to 2 parts by volume of glyoxylic acid is added, and 10mol/L of KOH is used for adjusting the pH of the reaction solution to 11.5 to 13.
8. The copper-zinc alloy composite material according to claim 1, wherein the zinc plating solution in the step (5) is obtained by: preparing a zinc chloride solution with the concentration of 0.6-0.8 g/ml, taking 400 parts of the zinc chloride solution by volume of raw materials, adding 30-35 parts of 2, 2-bipyridyl solution, adding zinc powder with the particle size of 100-300 mu m, and stirring to obtain the zinc plating solution.
9. The copper-zinc alloy composite material according to claim 1, wherein in the step (6), the copper-zinc plated graphite or carbon foam is freeze-dried for more than 5 hours, then placed in high-temperature silicone oil, heated to 240-280 ℃ to alloy the copper-zinc plating layer, after sufficient alloying, the sample is quenched into ice water, residual silicone oil on the surface of the sample is removed by using a detergent in an ultrasonic cleaning machine, and then the sample is washed by using a large amount of deionized water, and dried to obtain the copper-zinc alloy composite material.
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