CN104498917B - A kind of preparation method of copper facing Carbon foam - Google Patents
A kind of preparation method of copper facing Carbon foam Download PDFInfo
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- CN104498917B CN104498917B CN201410630949.XA CN201410630949A CN104498917B CN 104498917 B CN104498917 B CN 104498917B CN 201410630949 A CN201410630949 A CN 201410630949A CN 104498917 B CN104498917 B CN 104498917B
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- carbon foam
- vacuum
- ultrasound
- copper
- copper facing
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
-
- 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
- C23C18/1655—Process features
- C23C18/1664—Process features with additional means during the plating process
- C23C18/1666—Ultrasonics
-
- 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
- C23C18/1675—Process conditions
Abstract
The present invention relates to a kind of copper electroplating method of porous carbon material matrix, mainly a kind of preparation method of intermediate phase pitch-based copper facing Carbon foam.For this method using Mesophase Pitch-Derived Carbon Foam as matrix, the electroless copper method assisted altogether by vacuum ultrasonic is prepared for the uniform Carbon foam of copper facing in hole.The chemical plating that vacuum ultrasonic assists altogether carries out at room temperature, reduces the reaction temperature of chemical plating, and the simple process, it is at low cost, be easily industrialized production.Vacuum ultrasonic condition employed in copper facing Carbon foam preparation process of the present invention are as follows: the copper facing Carbon foam of different-thickness is made in ultrasound 80~130kHz, 100~180W, 0.01~10MPa of vacuum pressure, the cycle-index for passing through control vacuum ultrasonic.
Description
Technical field
The present invention relates to a kind of porous foam charcoal copper coatings, belong to porous carbon material process of surface treatment technology neck
Domain.
Background technique
Carbon foam is a kind of novel porous Carbon Materials, have low-density, high intensity, high heat-conductivity conducting, shock resistance, inhale wave,
The excellent properties such as noise reduction, resistant to chemical etching, low thermal coefficient of expansion, be widely used aerospace, the fields such as rocket steamer, such as
The large size heat of the shock resistance of the heat transfer exchange system, rocket of aerospace vehicle and satellite and noise abatement flat pad, chemical plant is handed over
The small-sized heat extraction device of parallel operation and computer device, in addition, apply also for catalyst carrier, adsorbent, filter device,
The fields such as biomaterial are a kind of novel charcoal materials with very big potentiality to be exploited and application prospect.However, with metal or high score
Sub- material is compared, and the mechanical property and heating conduction of Carbon foam are poor, this greatly limits Carbon foam it is further development and
Using.Current numerous researchers attempt to carry out coating modified research to Carbon foam, to obtain higher mechanical property, or compared with
The performances such as high surface area, thermal coefficient, conductivity.G.L.Vignoles et al. is by chemical vapor infiltration technology, in foam
SiC coating is carried out on carbon surface, the mechanical property as a result surveyed is greatly improved.Muklhopadhyay etc. passes through
The activity of plasma coating change foam carbon surface；Sourdiaucourt etc. realizes carbonization at 3000 DEG C by CVD method
Deposition of the hafnium in Carbon foam, enhances the mechanical performance of Carbon foam；M.Almajali etc. is by the method for electro-coppering in foam
Carbon surface copper facing, so that the mechanical property of Carbon foam and heating conduction improve；The above Carbon foam coating technology makes
Obtaining its mechanical property or electric conductivity has a degree of enhancing, however, existing technical method technique requires height, operation is multiple
Miscellaneous, cost is larger, and some has side effect to thermal conductivity and other performances.
Electroless copper technology does not need additional power source, and easy to operate simple process, coating is uniform, and porosity is low and appearance is good
It is good, and can be deposited on a variety of nonmetal basal bodies such as carbon material, and there is excellent covering property, high adhesive force is excellent to be resisted
Corrosion and wear-resisting property and excellent functional performance etc. and be rapidly developed it worldwide and widely
Using, and porous material lesser for aperture/hole depth, the method for conventional chemical plating can not achieve the gold-plated of its pore interior
Belong to, and conventional chemical plating needs for plating solution to be heated to certain temperature.
In order to realize foam carbon surface and intrapore homogeneous metal, so that the thermal conductivity and machinery of Carbon foam
Performance enhancement develops a kind of new chemical electroplating method and solves the problems, such as pore interior plating metal, realizes that Carbon foam is intrapore
Even copper facing will be significant.
Summary of the invention
The present invention is in the mechanical property and the poor defect of heating conduction and existing Carbon foam modification technology of Carbon foam
Deficiency, provides a kind of method of the electroless copper of foam carbon matrix, and this method keeps foam carbon surface modified, obtains overlay coating
Uniformly, the good matrix of binding force, and simple process and low cost, it is easy to accomplish industrialized production.The method successively include with
Lower step:
(1) oil removing → washing → roughening → washing → quick is successively carried out under sonic vacuum to Mesophase Pitch-Derived Carbon Foam
Change → washing → activation → washing.
Wherein, Carbon foam is Mesophase Pitch-Derived Carbon Foam in step (1), and percent opening is up to 20%~90%, pore diameter range
Between 50 μm~600 μm.
Wherein, it walks in poly- (1), oil removing is that Carbon foam is put into degreasing fluid, and heating water bath is to 55 DEG C, ultrasonic treatment
20min, is washed to neutrality, and degreasing fluid group becomes 60g/LNaOH, 20g/LNa2CO3, 20g/LNa3PO4, ultrasound condition is water-bath
80~130KHz of formula supersonic frequency, power 180W；Roughening is the nitre that the Carbon foam after oil removing is put into mass fraction and is 60%
In acid, it is ultrasonically treated 10min at normal temperature, ultrasound condition is that ultrasound condition is 80~130KHz of water-bath type supersonic frequency, rate
For 100~180W.
Sensitization be by roughening after Carbon foam be washed to neutrality after be put into sensitizing solution, vacuum sensitization 20min after go again from
10min, sensitization composition and condition: 5%HCl, 20g/LSnCl are impregnated in sub- water2And a small amount of tin grain, under room temperature, vacuum pressure
0.01~10MPa；
Activation, which refers to, is put into the Carbon foam after sensitization in activating solution, activating solution is placed in vacuum, activating solution active set
At and condition: mass concentration be 25g/LAgNO3 solution, normal-temperature reaction 25min；Vacuum pressure is 0.01~10MPa.
(2) deposition of Carbon foam copper coating layer
Carbon foam after surface active is added in chemical copper plating solution, sodium hydroxide and sulfuric acid solution adjusting pH are
11.5~12.5, bath temperature is room temperature, assists lower reaction to certain time altogether using intermittent ultrasound-vacuum, washs into
Property；The ultrasound condition are as follows: 20~130KHz, power are 100~180W, vacuum condition: 0.01~10MPa.
(3) copper facing Carbon foam carries out vacuum Passivation Treatment, and neutrality in the Carbon foam washing after copper facing is put into passivating solution
Wherein, in step (2), chemical bronze plating liquid includes 10~30g/L copper sulphate, 15~25mL/L formaldehyde, 15~30g/L
Sodium ethylene diamine tetracetate, 10~20g/L sodium tartrate, 10~20mL/L stabilizer, pH are 11.5~12.5, use chemically pure reagent
Solution is configured with deionized water；Chemical plating fluid is placed in vacuum chamber, with vacuum pump control the indoor pressure of vacuum be 0.01~
10MPa, vacuum chamber are placed in rinsing type ultrasound, and 80~130KHz of frequency, the power of intermittent ultrasound are 100~180W.
Using intermittent vacuum-ultrasonic circulation electroless copper, the first stage, vacuum, ultrasound alternately assistant chemical copper facing
It carries out, i.e., first the plating solution for being placed with Carbon foam is placed in ultrasound, react 3~20min, mechanical stirring 10min, is put into vacuum later
Indoor to react 10~20min under vacuum, second stage, vacuum-ultrasound is total to assistant chemical copper facing, i.e., by the elementary reaction
Plating solution is put into vacuum-ultrasound collective effect system afterwards, 80~130KHz, the ultrasound of 100~180W and 0.01~10MPa it is true
Electroless copper in empty common auxiliary Carbon foam hole wall, the intermittent every ultrasonic 3~5min of ultrasound stop 2~3min.
Wherein, it is molten to become the alcohol that mass fraction is 0.08~0.8% benzotriazole for the group of the passivating solution in step (3)
Liquid, Passivation Treatment is under sonic vacuum, 0.01~10MPa of vacuum pressure.
The present invention is deposited on Carbon foam outer surface and internal void wall by the electroless copper method that vacuum ultrasonic assists altogether
Uniform copper facing, the smooth careful densification of coating surface morphology, purity is higher, and ball shaped copper particles are uniform in size, and binding force is good,
Copper plate and Carbon foam are combined closely, so that the copper facing Carbon foam of preparation had both remained the excellent characteristic such as Carbon foam low-density,
But also with the performance of the high heat-conductivity conducting of fine copper, while copper facing is in Carbon foam ligament and breaking part deposition, connection, effective resistance
Crack arrest line is assembled in weak hole wall or the fault location being pre-stored in, and makes up foam carbon matrix rupture of ligament to frame strength
It influences, increases resistance of the foam carbon matrix in compression, and then increase the intensity of Carbon foam.Vacuum ultrasonic auxiliary of the present invention
Electroless copper is completed at room temperature, therefore reduces the temperature of reaction, the effect for playing energy conservation, reducing cost.
Detailed description of the invention
1. this method vacuum ultrasonic handles the SEM figure before and after Carbon foam substrate
Fig. 1 (a) is the SEM figure before Carbon foam chemical plating.
Fig. 1 (b) is the SEM figure of Carbon foam Carbon foam after the processing of intermittent vacuum ultrasonic, and Carbon foam hole steep that wall is by copper facing
Layer cladding completely, plated layer compact is uniform, and coating is well combined with matrix.
Carbon foam cross section SEM figure of Fig. 1 (c) Carbon foam after the processing of intermittent vacuum ultrasonic through resin embedding, foam
Charcoal pore wall is coated completely by copper, and is evenly coated.
2. Carbon foam electroless copper thickness SEM figure control under this method difference cycle-index
Fig. 2 (a) Carbon foam intermittence vacuum ultrasonic undergoes the thickness of coating SEM figure of Carbon foam after 3 circular treatments.
Fig. 2 (b) Carbon foam intermittence vacuum ultrasonic undergoes the thickness of coating SEM figure of Carbon foam after 5 circular treatments.
3. vacuum-stirring auxiliary Carbon foam electroless copper SEM figure
The SEM of Fig. 3 Carbon foam Carbon foam after vacuum machine stir process schemes, and Carbon foam hole alveolitoid is wrapped completely by copper plate
It covers, coating is coarse, and surface copper granular size is uneven, and there are serious agglomerations.
4. ultrasonic wave added Carbon foam electroless copper SEM schemes
The SEM figure of Fig. 4 Carbon foam Carbon foam after the processing of interval ultrasonic agitation, Carbon foam hole steep that wall is only on a small quantity by copper plate
Cladding, most of pore surface is still without copper deposition.
5. this method Experimental equipment, Fig. 5.
Specific embodiment
Embodiment one:
(1) 25.00mm × 25.00mm × 50.00mm size foam carbon matrix is placed in by 60g/LNaOH, 20g/
LNa2CO3, 20g/LNa3PO4In the degreasing fluid of composition, heating water bath is ultrasonically treated 20min, is washed to neutrality to 55 DEG C.
(2) oxidation processes are carried out to foam carbon surface, the Carbon foam after oil removing is put into the nitric acid that mass fraction is 60%
In, it is ultrasonically treated 10min at normal temperature, is washed to neutrality；Taking-up Carbon foam, which is placed in 100 DEG C of baking oven, to be dried to weight not
Become, weighing.
(3) sensitized treatment is carried out to Carbon foam, the Carbon foam after nitric acid oxidation is placed in by 5%HCl, 20g/LSnCl2And
In the sensitizing solution of a small amount of tin grain composition, it is put into after the vacuum chamber interior room temperature sensitiveization 20min of 0.01~0.1MPa of vacuum pressure
10min is impregnated in ionized water, is washed to neutrality.
(4) Carbon foam is activated, the Carbon foam after sensitization is placed in by 25g/LAgNO3The work of solution composition
Change in liquid, reacts 25min under normal-temperature vacuum；Vacuum pressure is 0.01~10MPa, is washed to neutrality.
(5) Carbon foam electroless copper: being put into 200mL by 20g/L copper sulphate for activated Carbon foam, 25mL/L formaldehyde,
25g/L sodium ethylene diamine tetracetate, 14g/L sodium tartrate, 20mL/L stabilizer composition plating solution in, with the molten adjusting of sodium hydroxide
The pH of plating solution is controlled 12.5, and plating solution is placed in vacuum chamber, and the indoor pressure of vacuum is 0.06MPa, at room temperature vacuum reaction
10min, then plating solution is placed in water-bath type ultrasound system, it is ultrasonic under 80~130KHz, 100~180W room temperature ultrasound condition
10mim, intermittent ultrasound, every ultrasonic 2~5min stop 1~3min, vacuum and ultrasound are carried out circulation later, electroless copper is added
In the process, after plating solution undergoes 5 circulations, foam carbon matrix is taken out from plating solution, is washed to neutrality, be 0.08 with mass fraction
The alcoholic solution vacuum of~0.8% benzotriazole is passivated 10min, is put into vacuum drying oven at a temperature of 90 °C, dry 4h
It takes out afterwards and weighs and carry out apparent, thickness and performance test, such as attached drawing 1 (b).
Embodiment two:
The implementation case from after plating solution undergoes 3 circulations in step (5) unlike case one, by foam carbon matrix from plating
It is taken out in liquid, is washed to neutrality, the alcoholic solution vacuum for the benzotriazole for being 0.08~0.8% with mass fraction is passivated
10min is put into vacuum drying oven at a temperature of 90 °C, is taken out after dry 4h and is weighed and carry out apparent, thickness and performance test,
Its step is identical as case study on implementation one as parameter, such as attached drawing 2.
Embodiment three:
Activated Carbon foam is put into 200mL by 20g/L sulfuric acid from step (5) unlike case one by the implementation case
Copper, 25mL/L formaldehyde, 25g/L sodium ethylene diamine tetracetate, 14g/L sodium tartrate, 20mL/L stabilizer composition plating solution in, use
The molten pH for adjusting plating solution of sodium hydroxide is controlled 12.5, and plating solution is placed in vacuum chamber, and the indoor pressure of vacuum is 0.06MPa,
Vacuum reaction 10min at room temperature carries out 400~800/min magnetic agitation, stirs 10min, later by vacuum and mechanical stirring into
Row circulation is added during electroless copper, after plating solution undergoes 5 circulations, foam carbon matrix is taken out from plating solution, is washed to
Property, with the alcoholic solution vacuum passivation 10min for the benzotriazole that mass fraction is 0.08~0.8%, being put into temperature is 90 DEG C
Vacuum drying oven in, taken out after dry 4h and weigh and carry out in apparent and performance test, other steps and parameter and case study on implementation
One is identical, such as attached drawing 3.
Example IV:
Activated Carbon foam is put into 200mL by 20g/L sulfuric acid from step (5) unlike case one by the implementation case
Copper, 25mL/L formaldehyde, 25g/L sodium ethylene diamine tetracetate, 14g/L sodium tartrate, 20mL/L stabilizer composition plating solution in, use
Plating solution is carried out 400~800r/min magnetic agitation, stirs 10min by the molten pH control for adjusting plating solution of sodium hydroxide 12.5, then
Plating solution is placed in water-bath type ultrasound system, the ultrasound 10mim under 80~130KHz, 100~180W room temperature ultrasound condition, interval
Property the every ultrasonic 2~5min of ultrasound, stop 1~3min, later carry out mechanical stirring and ultrasound during electroless copper is added in circulation,
After plating solution undergoes 5 circulations, foam carbon matrix is taken out from plating solution, is washed to neutrality, is 0.08~0.8% with mass fraction
The alcoholic solution vacuum of benzotriazole be passivated 10min, be put into vacuum drying oven at a temperature of 90 °C, take out and claim after dry 4h
It weighs and carries out in apparent and performance test, other steps are identical as case study on implementation one as parameter, such as attached drawing 4
Embodiment five:
Activated Carbon foam is put into 200mL by 20g/L sulfuric acid from step (5) unlike case one by the implementation case
Copper, 25mL/L formaldehyde, 25g/L sodium ethylene diamine tetracetate, 14g/L sodium tartrate, 20mL/L stabilizer composition plating solution in, use
The pH that sodium hydroxide solution adjusts plating solution is controlled 12.0, plating solution is placed in vacuum chamber, the indoor pressure of vacuum is
0.08MPa, at room temperature vacuum reaction 10min, then plating solution is placed in water-bath type ultrasound system, 80~130KHz, 100~
Ultrasound 10mim under 180W room temperature ultrasound condition, the intermittent every ultrasound 25min of ultrasound, stops 1~3min, later by vacuum and ultrasound
It carries out circulation to be added during electroless copper, after plating solution undergoes 5 circulations, foam carbon matrix is taken out from plating solution, is washed to
The alcoholic solution vacuum of neutrality, the benzotriazole for being 0.08~0.8% with mass fraction is passivated 10min, and being put into temperature is 90
DEG C vacuum drying oven in, taken out after dry 4h and weigh and carry out apparent and performance test, other steps and parameter and case study on implementation
One is identical.
Embodiment six:
From the pH of the plating solution unlike case one in step (5) control 12.0, vacuum pressure controls the implementation case
In 0.06MPa, other steps are identical as case study on implementation one as parameter；
Embodiment seven:
From the pH of the plating solution unlike case one in step (5) control 12.0, vacuum pressure controls the implementation case
In 0.1MPa, other steps are identical as case study on implementation one as parameter.
Claims (2)
1. a kind of preparation method of copper facing Carbon foam, which is characterized in that successively include the following steps:
(1) Mesophase Pitch-Derived Carbon Foam matrix is subjected to oil removing → washing → roughening → washing → sensitization under vacuum, ultrasound
→ washing → activation → water-washing pre-treatment, the porosity of Carbon foam 20%~90%, internal void diameter range is 50 μm~
600μm；
(2) deposition of Carbon foam copper coating layer
Carbon foam after surface active is added in chemical copper plating solution, adjusting pH is 11.5~12.5, and bath temperature is room
Temperature, using intermittent vacuum-ultrasonic circulation electroless copper: first stage, vacuum, ultrasound replace the progress of assistant chemical copper facing,
First the plating solution for being placed with Carbon foam is placed in ultrasound, reacts 3~20min, mechanical stirring 10min, is put into vacuum chamber later
10~20min is reacted under vacuum；Second stage, vacuum-ultrasound are total to assistant chemical copper facing, i.e., the plating after reacting the first stage
Liquid is put into vacuum-ultrasound collective effect system, and the vacuum of 80~130KHz, the ultrasound of 100~180W and 0.01~10MPa are total
With the electroless copper in auxiliary Carbon foam hole wall, the intermittent every ultrasonic 3~5min of ultrasound stops 2~3min；
(3) copper facing Carbon foam carries out vacuum Passivation Treatment, and the Carbon foam after copper facing is washed to neutrality and is put into passivating solution, is passivated
Processing is under sonic vacuum, 0.01~10MPa of vacuum pressure.
2. a kind of preparation method of copper facing Carbon foam according to claim 1, which is characterized in that in step (1),
The concrete operations of the oil removing are as follows: Carbon foam is put into degreasing fluid, to 30~55 DEG C, vacuum ultrasonic is handled heating water bath
20min, is washed to neutrality, and ultrasound condition is 80~130KHz of water-bath type supersonic frequency, power 180W, vacuum pressure 0.01
~10MPa；
The concrete operations of the roughening are as follows: the Carbon foam after oil removing is put into coarsening solution, is ultrasonically treated 10min at normal temperature,
Ultrasound condition is 80~130KHz of water-bath type supersonic frequency, power is 100~180W；
The concrete operations of the sensitization are as follows: be put into sensitizing solution after the Carbon foam after roughening is washed to neutrality, vacuum sensitization
It is going to impregnate 10min from Yu Shuizhong after 20min, under room temperature, vacuum pressure is 0.01~10MPa；
The concrete operations of the activation are as follows: the Carbon foam after sensitization is put into activating solution, activating solution is put into vacuum, room temperature
React 25min；Vacuum pressure is 0.01~10MP.
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| CN106583735B (en) * | 2016-12-22 | 2018-11-27 | 北京科技大学 | A method of it prepares with high-volume fractional diamond/copper composite material parts |
| CN109806664B (en) * | 2017-11-22 | 2022-03-04 | 辽宁省轻工科学研究院有限公司 | Preparation method of 1000 ℃ resistant metal high-temperature filter |
| CN110029330B (en) * | 2018-01-12 | 2021-04-20 | 中南大学 | Copper-zinc alloy composite material and preparation method thereof |
| CN108358185A (en) * | 2018-03-12 | 2018-08-03 | 江苏新亿源环保科技有限公司 | A kind of preparation method of toughening high heat conducting foam charcoal |
| CN115532258B (en) * | 2022-02-09 | 2023-07-21 | 青岛大学 | Preparation method and application of charcoal-based bionic catalytic material |
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|---|---|---|---|---|
| CN104076071A (en) * | 2013-12-19 | 2014-10-01 | 浙江工商大学 | Lupeose detection method based on foamy copper electrode |
| CN104087975A (en) * | 2013-12-19 | 2014-10-08 | 浙江工商大学 | Preparation method of foamed copper |
| CN104087778A (en) * | 2013-12-19 | 2014-10-08 | 浙江工商大学 | Preparation method of foamy copper for detection of sucrose concentration |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104076071A (en) * | 2013-12-19 | 2014-10-01 | 浙江工商大学 | Lupeose detection method based on foamy copper electrode |
| CN104087975A (en) * | 2013-12-19 | 2014-10-08 | 浙江工商大学 | Preparation method of foamed copper |
| CN104087778A (en) * | 2013-12-19 | 2014-10-08 | 浙江工商大学 | Preparation method of foamy copper for detection of sucrose concentration |
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