CN110029330A - A kind of ormolu composite material and preparation method - Google Patents

A kind of ormolu composite material and preparation method Download PDF

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CN110029330A
CN110029330A CN201810031498.6A CN201810031498A CN110029330A CN 110029330 A CN110029330 A CN 110029330A CN 201810031498 A CN201810031498 A CN 201810031498A CN 110029330 A CN110029330 A CN 110029330A
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graphite
ormolu
copper
carbon foam
zinc
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CN110029330B (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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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

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Abstract

The invention discloses a kind of ormolu composite materials, it is made of the ormolu layer on graphite or Carbon foam and its surface layer, the ormolu layer is obtained by copper coating and zinc coating through Alloying Treatment, the ormolu layer is made of by weight percentage following components: copper 40%~80%, zinc 20%~60%.Ormolu composite material of the present invention uses graphite or Carbon foam for substrate, possesses biggish specific surface area, has very strong adsorptivity, can remove chlorine, chlorine ammonia and some other organic substance, and synergistic effect is generated between ormolu layer and graphite or Carbon foam；The present invention passes through modulation process parameter, the ormolu layer of available difference grain size, purity is high, coating is uniform, and thickness is controllable, and gained ormolu layer and graphite or the interface cohesion of Carbon foam are good, and the contact angle of alloyed layer and water and glycerol is small, has good wetability；Present invention process method is simple, low in cost, not high to equipment requirement, can be suitable for large-scale production.

Description

A kind of ormolu composite material and preparation method
Technical field
The invention belongs to technical field of material, and in particular to a kind of ormolu composite material and preparation method.
Background technique
Ormolu (Kinetic Degradation Fluxion, abbreviation KDF) is American scientist Don Heskett For doctor in a kind of novel water filtering medium of invention in 1984, the water purifying principle of KDF is to carry out water by electrochemical oxidation-reduction Processing, can inhibit bacteria breed, the pollutants such as heavy metal, chlorine and hydrogen sulfide in water removal, and its long service life be gone, in water Process field is widelyd popularize, but its adsorption capacity is not strong, exclusive use it is ineffective, it is mostly straight with active carbon particle Connect and be used in mixed way, be easy to appear particle occluding device pipeline, cause the waste of a large amount of filtering materials, and increase maintenance at This.
Currently, the preparation of ormolu layer, mainly using arc spraying technology, the ormolu layer being prepared is pure Degree is not high, and uneven coating is even, and technique requirement, in actual use, copper meeting and water is not achieved in the refining level of especially copper In oxidizing substance react, generate the compound and complex compound of copper, cause copper ion in water exceeded, there are in heavy metal The potential danger of poison.
Summary of the invention
The purpose of the present invention is to provide one kind, to be not easy to plug equipment pipe, purity is high, coating uniform low-cost Ormolu composite material and preparation method.
A kind of ormolu composite material of the present invention, by matrix graphite or Carbon foam and its ormolu layer structure on surface layer At the ormolu layer is obtained by copper coating and zinc coating through Alloying Treatment, and the ormolu layer is pressed by following components Weight percent composition: copper 40%~80%, zinc 20%~60%.
Preferably, the ormolu layer with a thickness of 2~40 μm；It is furthermore preferred that the ormolu layer with a thickness of 5 ~20 μm.
The present invention also provides a kind of preparation methods of ormolu composite material, comprising the following steps:
(1) acid processing: graphite or Carbon foam are put into the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid and are ultrasonically treated, cleaned up After obtain acid treated graphite or Carbon foam；
(2) sensitized treatment: taking stannous chloride to be dissolved in concentrated hydrochloric acid, sensitizing solution obtained after dilution, then will be obtained by step (1) Acid treated graphite or Carbon foam are added in sensitizing solution and are ultrasonically treated, and the graphite or foam of sensitized treatment are obtained after cleaning up Charcoal；
(3) it is activated: taking palladium chloride to be dissolved in concentrated hydrochloric acid, activating solution is obtained after dilution, it then will be quick obtained by step (2) The graphite or Carbon foam for changing processing are added in activating solution and are ultrasonically treated, the graphite or foam being activated after cleaning up Charcoal；
(4) graphite or Carbon foam that are activated obtained by step (3) graphite or Carbon foam copper coating: are added to copper plating In liquid, and bipyridyl is added as stabilizer, plating solution is heated, glyoxalic acid is then added as reducing agent, adjusts PH, reaction one Graphite or Carbon foam are taken out after fixing time, copper-plated graphite or Carbon foam are obtained after cleaning up；
(5) graphite or foam carbon surface are zinc-plated: copper-plated graphite or Carbon foam obtained by step (4) are added to zinc plating solution In, be warming up to boiling, reaction after a certain period of time takes out graphite or Carbon foam, obtained after cleaning up plated copper zinc graphite or Carbon foam；
(6) Alloying Treatment of copper zinc coating: the graphite of plated copper zinc obtained by step (5) or Carbon foam is chilled dry It is dry, 240~280 DEG C are then heated to, so that the alloying of copper zinc coating, is then quenched, is obtained after cleaned, dry To ormolu composite material.
The volume ratio of the concentrated sulfuric acid and concentrated nitric acid is (2~4) in the step (1): 1.
The mass volume ratio of stannous chloride and concentrated hydrochloric acid is 1:1g/ml in the step (2), and the quality of the concentrated hydrochloric acid is dense Degree is 36~38%, and raw material takes the concentrated hydrochloric acid solution of 2~3 parts of stannous chlorides based on parts by volume, is diluted with water to 100 parts, obtains Sensitizing solution.
The mass volume ratio of palladium chloride and concentrated hydrochloric acid is 1:20g/ml in the step (3), and the quality of the concentrated hydrochloric acid is dense Degree is 36~38%, and raw material takes the concentrated hydrochloric acid solution of 1~3 part of palladium chloride based on parts by volume, is diluted with water to 100 parts, is lived Change liquid.
Copper electrolyte in the step (4), is obtained by following manner: raw material by weight, weighs 25~35 parts CuSO4·5H2O, 70~90 parts of EDTANa2, 25~30 parts of NaKC4H4O6·4H2O, 30~35 parts of KOH, is dissolved in 400 In~450 parts of water, copper electrolyte is obtained after mixing evenly.The EDTANa2And NaKC4H4O6As complexing agent, with copper ion network Prevent copper ion from generating precipitating after conjunction.
In the step (4), raw material takes 20~30 parts of copper electrolytes based on parts by volume, and 10~15 parts of 2,2- bipyridyls are added Solution, bipyridyl solution concentration are (0.1~0.3g)/100ml, are then diluted with water to 80~100 parts, step is then added (3) plating solution is heated to 55~65 DEG C using water-bath, 1~2 part of glyoxalic acid is added by the graphite or Carbon foam that gained is activated, The pH to 11.5~13 of reaction solution is adjusted using the KOH of 10mol/L.The 2,2- bipyridyl is as the stabilization in copper facing reaction Agent can make bath stability, and adjust the size of copper facing crystal grain, make crystal grain refinement.
Zinc plating solution in the step (5), is obtained by following manner: compound concentration is that the zinc chloride of 0.6~0.8g/ml is molten Liquid, raw material take 400 parts of liquor zinci chloridis based on parts by volume, add 30~35 parts of 2,2- bipyridyl solutions, and it is 100 that partial size, which is added, The zinc powder of~300um obtains silver gray turbid, i.e. zinc plating solution after stirring.
In the step (6), by the graphite of plated copper zinc or the freeze-dried 5h or more of Carbon foam, it is then placed in high temperature silicon In oil, 240~280 DEG C are heated to, the reaction time is 2~3h, makes the alloying of copper zinc coating, will after abundant alloying Sample is quenched into ice water, with the silicone oil of abluent removal sample surfaces remnants in supersonic cleaning machine, then with a large amount of deionizations Water rinses, and obtains surface ormolu composite material after dry.
Compared with prior art, advantageous effects of the invention are as follows:
(1) ormolu composite material of the present invention uses graphite or Carbon foam for substrate, possesses biggish specific surface area, tool There is very strong adsorptivity, chlorine, chlorine ammonia and some other organic substance can be removed, between ormolu layer and graphite or Carbon foam Synergistic effect is generated, ormolu layer can inhibit bacteria breed by electrochemical oxidation-reduction principle, remove weight in water removal The pollutants such as metal, hydrogen sulfide improve water purification ability, and its long service life, are not easy to plug equipment pipe, are a kind of ideal Water purification filtration layer material.
(2) for the present invention by modulation process parameter, the ormolu layer of available difference grain size is with high purity, Coating is uniform, and thickness is controllable, and gained ormolu layer and graphite or the interface cohesion of Carbon foam are good, and alloyed layer and water and The contact angle of glycerol is small, has good wetability.
(3) present invention process method is simple, low in cost, not high to equipment requirement, can be suitable for large-scale production.
Detailed description of the invention
Exterior appearance and scanning electron microscope (SEM) photograph after the 1 sample copper facing of Fig. 1 embodiment of the present invention.
Exterior appearance and scanning electron microscope (SEM) photograph after 1 sample of Fig. 2 embodiment of the present invention is zinc-plated.
Exterior appearance and scanning electron microscope (SEM) photograph after 1 sample alloy of Fig. 3 embodiment of the present invention.
Picture of 1 water droplet of Fig. 4 embodiment of the present invention in ormolu layer surface.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation Example is only a part of the embodiment of the present invention, rather than whole embodiments, based on the embodiments of the present invention, the common skill in this field Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects It encloses.
Embodiment 1
A kind of preparation method of ormolu composite material of the present invention, comprising the following steps:
(1) acid processing: use high purity graphite rod for matrix, graphite rod is having a size of long 50mm, wide 5mm, high 5mm, by graphite Stick, which is put into the mixed liquor (volume ratio 3:1) of the concentrated sulfuric acid and concentrated nitric acid, is ultrasonically treated 10min, is cleaned with a large amount of deionized waters dry Only, acid treated graphite rod is obtained；
(2) it sensitized treatment: weighs 2.5g stannous chloride and is dissolved in 2.5ml concentrated hydrochloric acid (mass concentration 36%), add water dilute It releases to 100ml, obtains sensitizing solution, then treated that graphite rod is added in sensitizing solution is ultrasonically treated by acid obtained by step (1) 10min is cleaned up with a large amount of deionized waters, obtains the graphite rod of sensitized treatment；
(3) it is activated: weighing 0.25g palladium chloride and be dissolved in 5ml concentrated hydrochloric acid (mass concentration 36%), be diluted with water to 250ml obtains activating solution, and then the graphite rod of sensitized treatment obtained by step (2) is added in activating solution and is ultrasonically treated 10min is cleaned up with a large amount of deionized waters, the graphite rod being activated；
(4) graphite rod copper coating: the graphite rod being activated obtained by step (3) is added in 25ml copper electrolyte, is added Entering 2, the 2- bipyridyl of 12ml as stabilizer, bipyridyl solution concentration is 0.2g/100ml, it is then diluted with water to 90ml, The temperature of plating solution is heated to 60 DEG C in water-bath, 1.5ml glyoxalic acid is added as reducing agent, using the KOH concentrated solution of 10mol/L PH to 12 is adjusted, starts timing after red occurs in graphite rod surface, takes out after 8min, cleaned up with a large amount of deionized waters To copper-plated graphite rod, sample appearance pattern and scanning electron microscopic picture after copper facing are shown in Fig. 1；
The preparation of the copper electrolyte: 500ml copper plating bath is prepared with volumetric flask, sequentially adds following drug: 30g CuSO4· 5H2O；80g EDTANa2；28g NaKC4H4O6·4H2O；34g KOH finally adds water to 500ml；
(5) graphite rod surface is zinc-plated: copper-plated graphite rod obtained by step (4) being added in 150ml zinc plating solution, is warming up to Graphite rod is taken out after reacting 8min, is cleaned up with a large amount of deionized waters, obtain the graphite rod of plated copper zinc by boiling, zinc-plated Sample appearance pattern and scanning electron microscopic picture afterwards is shown in Fig. 2；
The preparation of the zinc plating solution: 280g ZnCl is weighed2In beaker, 400ml is added water to, 32ml is added in stirring and dissolving 2,2- bipyridyls as stabilizer, then plus 2g zinc powder (partial size be 100~300um), stir evenly, obtain silver gray turbid；
(6) Alloying Treatment of copper zinc coating: by the freeze-dried 6h of graphite rod of plated copper zinc obtained by step (5), so 240 DEG C are heated in silicone oil bath afterwards, so that copper zinc coating alloying 2h, sample is quenched into ice water, in supersonic cleaning machine The middle silicone oil with abluent removal sample surfaces remnants, then rinsed with a large amount of deionized waters, coating surface copper zinc is obtained after dry The graphite rod of alloy-layer, sample appearance pattern and scanning electron microscopic picture after alloying are shown in Fig. 3, institute's plated copper zinc in the present embodiment Alloy-layer structural parameters and performance are as shown in table 1.
By Fig. 1-3 it is found that the copper facing of the present embodiment, zinc coat and ormolu layer even compact, and coat intact, water droplet See that Fig. 4, ormolu layer are good with wettability in the shape of ormolu layer surface.As can be seen from Table 1, in ormolu layer Ingredient are as follows: copper 50wt%, zinc 50wt%；Alloy-layer with a thickness of 10 μm, crystallite dimension is smaller, be 225nm；Tape Test result Show that binding force is strong between alloy-layer and substrate, alloy-layer is not easily to fall off in use；In addition, alloy-layer and ionized water and The contact angle of glycerol is smaller, respectively 61.22 ° and 86.68 °, illustrate the alloy-layer can with most of process object aqueous solution it Between there are affine interface, this is conducive to the sewage treatment capacity for promoting alloy-layer.
1 the present embodiment high purity graphite rod coating surface ormolu layer structural parameters of table and performance
Embodiment 2
A kind of preparation method of ormolu composite material of the present invention, comprising the following steps:
(1) acid processing: use high purity graphite rod for matrix, graphite rod is having a size of long 50mm, wide 5mm, high 5mm, by graphite Stick, which is put into the mixed liquor (volume ratio 2:1) of the concentrated sulfuric acid and concentrated nitric acid, is ultrasonically treated 10min, is cleaned with a large amount of deionized waters dry Only, acid treated graphite rod is obtained；
(2) it sensitized treatment: weighs 2.5g stannous chloride and is dissolved in 2.5ml concentrated hydrochloric acid (mass concentration 36%), add water dilute It releases to 100ml, obtains sensitizing solution, then treated that graphite rod is added in sensitizing solution is ultrasonically treated by acid obtained by step (1) 10min is cleaned up with a large amount of deionized waters, obtains the graphite rod of sensitized treatment；
(3) it is activated: weighing 0.25g palladium chloride and be dissolved in 5ml concentrated hydrochloric acid (mass concentration 36%), be diluted with water to 250ml obtains activating solution, and then the graphite rod of sensitized treatment obtained by step (2) is added in activating solution and is ultrasonically treated 10min is cleaned up with a large amount of deionized waters, the graphite rod being activated；
(4) graphite rod copper coating: the graphite rod being activated obtained by step (3) is added in 25ml copper electrolyte (same Embodiment 1), 2, the 2- bipyridyl of 12ml is added as stabilizer, 100ml is then diluted with water to, in a water bath by plating solution Temperature is heated to 60 DEG C, and 1.5ml glyoxalic acid is added as reducing agent, adjusts PH to 12, stone using the KOH concentrated solution of 10mol/L Inker surface starts timing after there is red, takes out after 4min, is cleaned up to obtain copper-plated graphite rod with a large amount of deionized waters；
(5) graphite rod surface is zinc-plated: copper-plated graphite rod obtained by step (4) is added in 150ml zinc plating solution (with implementation Example 1), it is warming up to boiling, graphite rod is taken out after reacting 8min, is cleaned up with a large amount of deionized waters, obtains plated copper zinc Graphite rod；
(6) Alloying Treatment of copper zinc coating: by the freeze-dried 6h of graphite rod of plated copper zinc obtained by step (5), so 250 DEG C are heated in silicone oil bath afterwards, so that copper zinc coating alloying 2h, sample is quenched into ice water, in supersonic cleaning machine The middle silicone oil with abluent removal sample surfaces remnants, then rinsed with a large amount of deionized waters, coating surface copper zinc is obtained after dry The graphite rod of alloy-layer, institute's plated copper zinc alloy layer structural parameters and performance are as shown in table 2 in the present embodiment.
2 the present embodiment high purity graphite rod coating surface ormolu layer structural parameters of table and performance
As can be seen from Table 2, ingredient in ormolu layer are as follows: copper 40wt%, zinc 60wt%；Alloy-layer with a thickness of 8 μm, Crystallite dimension is smaller, is 208nm；The result shows that binding force is strong between alloy-layer and substrate, alloy-layer was using Tape Test It is not easily to fall off in journey；In addition, the contact angle of alloy-layer and ionized water and glycerol is respectively 72.33 ° and 88.84 °, illustrate the alloy Layer can there are affine interfaces between most of process object aqueous solution, this is conducive to the sewage treatment capacity for promoting alloy-layer.
Embodiment 3
A kind of preparation method of ormolu composite material of the present invention, comprising the following steps:
(1) acid processing: use high purity graphite rod for matrix, graphite rod is having a size of long 50mm, wide 5mm, high 5mm, by graphite Stick, which is put into the mixed liquor (volume ratio 3:1) of the concentrated sulfuric acid and concentrated nitric acid, is ultrasonically treated 10min, is cleaned with a large amount of deionized waters dry Only, acid treated graphite rod is obtained；
(2) it sensitized treatment: weighs 2.5g stannous chloride and is dissolved in 2.5ml concentrated hydrochloric acid (mass concentration 36%), add water dilute It releases to 100ml, obtains sensitizing solution, then treated that graphite rod is added in sensitizing solution is ultrasonically treated by acid obtained by step (1) 10min is cleaned up with a large amount of deionized waters, obtains the graphite rod of sensitized treatment；
(3) it is activated: weighing 0.25g palladium chloride and be dissolved in 5ml concentrated hydrochloric acid (mass concentration 36%), be diluted with water to 250ml obtains activating solution, and then the graphite rod of sensitized treatment obtained by step (2) is added in activating solution and is ultrasonically treated 10min is cleaned up with a large amount of deionized waters, the graphite rod being activated；
(4) graphite rod copper coating: the graphite rod being activated obtained by step (3) is added in 25ml copper electrolyte (same Embodiment 1), 2, the 2- bipyridyl of 12ml is added as stabilizer, 90ml is then diluted with water to, in a water bath by the temperature of plating solution Degree is heated to 60 DEG C, and 1.5ml glyoxalic acid is added as reducing agent, adjusts PH to 12, graphite using the KOH concentrated solution of 10mol/L Stick surface starts timing after there is red, takes out after 8min, is cleaned up to obtain copper-plated graphite rod with a large amount of deionized waters；
(5) graphite rod surface is zinc-plated: copper-plated graphite rod obtained by step (4) is added in 150ml zinc plating solution (with implementation Example 1), it is warming up to boiling, graphite rod is taken out after reacting 1min, is cleaned up with a large amount of deionized waters, obtains plated copper zinc Graphite rod；
(6) Alloying Treatment of copper zinc coating: by the freeze-dried 6h of graphite rod of plated copper zinc obtained by step (5), so 240 DEG C are heated in silicone oil bath afterwards, so that copper zinc coating alloying 2h, sample is quenched into ice water, in supersonic cleaning machine The middle silicone oil with abluent removal sample surfaces remnants, then rinsed with a large amount of deionized waters, coating surface copper zinc is obtained after dry The graphite rod of alloy-layer, institute's plated copper zinc alloy layer structural parameters and performance are as shown in table 3 in the present embodiment.
3 the present embodiment high purity graphite rod coating surface ormolu layer structural parameters of table and performance
As can be seen from Table 3, ingredient in ormolu layer are as follows: copper 80wt%, zinc 20wt%；Alloy-layer with a thickness of 5 μm, Crystallite dimension is smaller, is 225nm；The result shows that binding force is strong between alloy-layer and substrate, alloy-layer was using Tape Test It is not easily to fall off in journey；In addition, the contact angle of alloy-layer and ionized water and glycerol is respectively 59.37 ° and 83.27 °, illustrate the alloy Layer can there are affine interfaces between most of process object aqueous solution, this is conducive to the sewage treatment capacity for promoting alloy-layer.
Embodiment 4
A kind of preparation method of ormolu composite material of the present invention, comprising the following steps:
(1) acid processing: use high purity graphite plate for matrix, graphite plate is having a size of long 50mm, wide 50mm, thickness 5mm, by stone Inker, which is put into the mixed liquor (volume ratio 3:1) of the concentrated sulfuric acid and concentrated nitric acid, is ultrasonically treated 10min, is cleaned with a large amount of deionized waters Completely, acid treated graphite rod is obtained；
(2) it sensitized treatment: weighs 2.5g stannous chloride and is dissolved in 2.5ml concentrated hydrochloric acid (mass concentration 36%), add water dilute It releases to 100ml, obtains sensitizing solution, then treated that graphite plate is added in sensitizing solution is ultrasonically treated by acid obtained by step (1) 10min is cleaned up with a large amount of deionized waters, obtains the graphite rod of sensitized treatment；
(3) it is activated: weighing 0.25g palladium chloride and be dissolved in 5ml concentrated hydrochloric acid (mass concentration 36%), be diluted with water to 250ml obtains activating solution, and then the graphite plate of sensitized treatment obtained by step (2) is added in activating solution and is ultrasonically treated 10min is cleaned up with a large amount of deionized waters, the graphite plate being activated；
(4) graphite plate copper coating: the graphite plate being activated obtained by step (3) is added in 25ml copper electrolyte (same Embodiment 1), 2, the 2- bipyridyl of 6ml is added as stabilizer, 90ml is then diluted with water to, in a water bath by the temperature of plating solution Degree is heated to 60 DEG C, and 1.5ml glyoxalic acid is added as reducing agent, adjusts PH to 12.5, stone using the KOH concentrated solution of 10mol/L Black plate surface starts timing after there is red, takes out after 8min, is cleaned up to obtain copper-plated graphite plate with a large amount of deionized waters；
(5) graphite plate surface is zinc-plated: copper-plated graphite plate obtained by step (4) is added in 150ml zinc plating solution (with implementation Example 1), it is warming up to boiling, graphite plate is taken out after reacting 8min, is cleaned up with a large amount of deionized waters, obtains plated copper zinc Graphite plate；
(6) Alloying Treatment of copper zinc coating: by the freeze-dried 6h of graphite plate of plated copper zinc obtained by step (5), so 260 DEG C are heated in silicone oil bath afterwards, so that copper zinc coating alloying 2h, sample is quenched into ice water, in supersonic cleaning machine The middle silicone oil with abluent removal sample surfaces remnants, then rinsed with a large amount of deionized waters, coating surface copper zinc is obtained after dry The graphite plate of alloy-layer, institute's plated copper zinc alloy layer structural parameters and performance are as shown in table 4 in the present embodiment.
4 the present embodiment high purity graphite plate surface plated copper zinc alloy layer structural parameters of table and performance
As can be seen from Table 4, ingredient in ormolu layer are as follows: copper 50wt%, zinc 50wt%；Alloy-layer with a thickness of 10 μ M, crystallite dimension 413nm；Tape Test is the result shows that binding force is strong between alloy-layer and substrate, and alloy-layer is in use It is not easily to fall off；In addition, the contact angle of alloy-layer and ionized water and glycerol is respectively 55.35 ° and 85.20 °, illustrate the alloy-layer energy There are affine interfaces between most of process object aqueous solution, this is conducive to the sewage treatment capacity for promoting alloy-layer.
Embodiment 5
A kind of preparation method of ormolu composite material of the present invention, comprising the following steps:
(1) acid processing: use Carbon foam for matrix, Carbon foam puts Carbon foam having a size of long 50mm, wide 50mm, high 5mm Enter and be ultrasonically treated 10min in the mixed liquor (volume ratio 2:1) of the concentrated sulfuric acid and concentrated nitric acid, is cleaned up with a large amount of deionized waters, Obtain acid treated Carbon foam；
(2) it sensitized treatment: weighs 2.5g stannous chloride and is dissolved in 2.5ml concentrated hydrochloric acid (mass concentration 36%), add water dilute It releases to 100ml, obtains sensitizing solution, then treated that Carbon foam is added in sensitizing solution is ultrasonically treated by acid obtained by step (1) 10min is cleaned up with a large amount of deionized waters, obtains the Carbon foam of sensitized treatment；
(3) it is activated: weighing 0.25g palladium chloride and be dissolved in 5ml concentrated hydrochloric acid (mass concentration 36%), be diluted with water to 250ml obtains activating solution, and then the Carbon foam of sensitized treatment obtained by step (2) is added in activating solution and is ultrasonically treated 10min is cleaned up with a large amount of deionized waters, the Carbon foam being activated；
(4) Carbon foam copper coating: the Carbon foam being activated obtained by step (3) is added in 25ml copper electrolyte (same Embodiment 1), 2, the 2- bipyridyl of 12ml is added as stabilizer, 90ml is then diluted with water to, in a water bath by the temperature of plating solution Degree is heated to 60 DEG C, and 1.5ml glyoxalic acid is added as reducing agent, adjusts PH to 12.5, bubble using the KOH concentrated solution of 10mol/L Foam carbon surface starts timing after there is red, takes out after 18min, is cleaned up to obtain copper-plated foam with a large amount of deionized waters Charcoal；
(5) foam carbon surface is zinc-plated: copper-plated Carbon foam obtained by step (4) being added in 150ml zinc plating solution, is warming up to Carbon foam is taken out after reacting 12min, is cleaned up with a large amount of deionized waters, obtain the Carbon foam of plated copper zinc by boiling；
The preparation of the zinc plating solution: 280g ZnCl is weighed2In beaker, 400ml is added water to, 32ml is added in stirring and dissolving 2,2- bipyridyls as stabilizer, then plus 4g zinc powder (partial size be 100~300um), stir evenly, obtain silver gray turbid；
(6) Alloying Treatment of copper zinc coating: by the freeze-dried 6h of Carbon foam of plated copper zinc obtained by step (5), so 250 DEG C are heated in silicone oil bath afterwards, so that copper zinc coating alloying 2h, sample is quenched into ice water, in supersonic cleaning machine The middle silicone oil with abluent removal sample surfaces remnants, then rinsed with a large amount of deionized waters, coating surface copper zinc is obtained after dry The Carbon foam of alloy-layer, institute's plated copper zinc alloy layer structural parameters and performance are as shown in table 5 in the present embodiment.
5 the present embodiment Carbon foam coating surface ormolu layer structural parameters of table and performance
As can be seen from Table 5, ingredient in ormolu layer are as follows: copper 50wt%, zinc 50wt%；Alloy-layer with a thickness of 20 μ M, crystallite dimension 235nm；The result shows that binding force is strong between alloy-layer and base foam charcoal, alloy-layer is using Tape Test It is not easily to fall off in the process；In addition, the contact angle of alloy-layer and ionized water and glycerol is respectively 64.18 ° and 86.42 °, illustrate the conjunction There are affine interfaces between layer gold energy and most of process object aqueous solution, this is conducive to the sewage treatment energy for promoting alloy-layer Power.The present invention uses graphite or Carbon foam for substrate, and electroless copper, electroless zinc plating, Alloying Treatment, by copper are then carried out to it Zinc alloy layer is plated to graphite or foam carbon surface, and purity is high, coating is uniform, and thickness is controllable, at low cost, can be used as ideal Water-purifying material.

Claims (10)

1. a kind of ormolu composite material, which is characterized in that by matrix graphite or Carbon foam and its ormolu layer on surface layer It constitutes, the ormolu layer is obtained by copper coating and zinc coating through Alloying Treatment, and the ormolu layer is by following components It forms by weight percentage: copper 40%~80%, zinc 20%~60%.
2. ormolu composite material according to claim 1, which is characterized in that the ormolu layer with a thickness of 2 ~40 μm.
3. a kind of preparation method of ormolu composite material according to claim 1 or 2, comprising the following steps:
(1) acid processing: graphite or Carbon foam being put into the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid and are ultrasonically treated, after cleaning up To acid treated graphite or Carbon foam；
(2) sensitized treatment: taking stannous chloride to be dissolved in concentrated hydrochloric acid, sensitizing solution obtained after dilution, then will be at acid obtained by step (1) Graphite or Carbon foam after reason, which are added in sensitizing solution, to be ultrasonically treated, and the graphite or Carbon foam of sensitized treatment are obtained after cleaning up；
(3) it is activated: taking palladium chloride to be dissolved in concentrated hydrochloric acid, activating solution is obtained after dilution, it then will be at sensitization obtained by step (2) The graphite or Carbon foam of reason, which are added in activating solution, to be ultrasonically treated, the graphite or Carbon foam being activated after cleaning up；
(4) graphite or Carbon foam that are activated obtained by step (3) graphite or Carbon foam copper coating: are added to copper electrolyte In, and bipyridyl is added as stabilizer, plating solution is heated, glyoxalic acid is then added as reducing agent, adjusts PH, reaction is certain Graphite or Carbon foam are taken out after time, copper-plated graphite or Carbon foam are obtained after cleaning up；
(5) graphite or foam carbon surface are zinc-plated: copper-plated graphite or Carbon foam obtained by step (4) being added in zinc plating solution, risen Temperature to boiling, after a certain period of time take out graphite or Carbon foam by reaction, and the graphite or foam of plated copper zinc are obtained after cleaning up Charcoal；
(6) Alloying Treatment of copper zinc coating: the graphite of plated copper zinc obtained by step (5) or Carbon foam is freeze-dried, so After be heated to 240~280 DEG C so that the alloying of copper zinc coating, is then quenched, obtain copper after cleaned, dry Zinc alloy composites.
4. the preparation method of ormolu composite material according to claim 3, which is characterized in that in the step (1) The volume ratio of the concentrated sulfuric acid and concentrated nitric acid is (2~4): 1.
5. the preparation method of ormolu composite material according to claim 3, which is characterized in that in the step (2) The mass volume ratio of stannous chloride and concentrated hydrochloric acid is 1:1g/ml, and the mass concentration of the concentrated hydrochloric acid is 36~38%, and raw material presses body Product part meter, takes the concentrated hydrochloric acid solution of 2~3 parts of stannous chlorides, is diluted with water to 100 parts, obtains sensitizing solution.
6. the preparation method of ormolu composite material according to claim 3, which is characterized in that in the step (3) The mass volume ratio of palladium chloride and concentrated hydrochloric acid is 1:20g/ml, and the mass concentration of the concentrated hydrochloric acid is 36~38%, and raw material presses body Product part meter, takes the concentrated hydrochloric acid solution of 1~3 part of palladium chloride, is diluted with water to 100 parts, obtains activating solution.
7. the preparation method of ormolu composite material according to claim 3, which is characterized in that in the step (4) Copper electrolyte is obtained by following manner: raw material by weight, weighs 25~35 parts of CuSO4·5H2O, 70~90 parts EDTANa2, 25~30 parts of NaKC4H4O6·4H2O, 30~35 parts of KOH are dissolved in 400~450 parts of water, stir evenly After obtain copper electrolyte.
8. the preparation method of ormolu composite material according to claim 3, which is characterized in that in the step (4), Raw material takes 20~30 parts of copper electrolytes based on parts by volume, and 10~15 parts of 2,2- bipyridyl solutions are added, and bipyridyl solution concentration is Then (0.1~0.3g)/100ml is diluted with water to 80~100 parts, add the graphite or bubble being activated obtained by step (3) Foam charcoal, is heated to 55~65 DEG C for plating solution using water-bath, 1~2 part of glyoxalic acid is added, and adjusts reaction solution using the KOH of 10mol/L PH to 11.5~13.
9. the preparation method of ormolu composite material according to claim 3, which is characterized in that in the step (5) Zinc plating solution, is obtained by following manner: compound concentration is the liquor zinci chloridi of 0.6~0.8g/ml, and raw material takes 400 based on parts by volume Part liquor zinci chloridi, adds 30~35 parts of 2,2- bipyridyl solutions, and the zinc powder that partial size is 100~300um is added, obtains after stirring Zinc plating solution.
10. the preparation method of ormolu composite material according to claim 3, which is characterized in that the step (6) In, by the graphite of plated copper zinc or the freeze-dried 5h or more of Carbon foam, it is then placed in high-temperature silicon oil, is heated to 240~280 DEG C, so that sample is quenched into ice water by the alloying of copper zinc coating after abundant alloying, used in supersonic cleaning machine Abluent removes the silicone oil of sample surfaces remnants, then is rinsed with a large amount of deionized waters, obtains ormolu composite material after dry.
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