CN106811778A - The preparation and palladium-copper alloy film and application of component and the controllable palladium-copper alloy film of thickness - Google Patents
The preparation and palladium-copper alloy film and application of component and the controllable palladium-copper alloy film of thickness Download PDFInfo
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Abstract
The present invention relates to the preparation and palladium-copper alloy film and application of the controllable palladium-copper alloy film of a kind of component and thickness, using layering electric plating method, successively alternating deposit Metal Palladium and copper on carrier to be plated, the metal thickness of every layer of sub-control system and the amount of material, final high-temperature alloy, forms fine and close palladium-copper alloy film.The method reaches the Metal Palladium and copper of accurate deposition respective amount by the control to the system quantity of electric charge, and then reaches the purpose of control alloy membrane component.Another to control the quality of film by regulating and controlling current density, the quantity of electric charge of adjustment and control system different phase controls the composition of palladium-copper alloy film, and then reaches the regulation and control to alloy film thickness.The present invention breaks through traditional chemical plating, and every layer of limitation for being required to alloying step breaches the limitation of metal reduction potential, realize deposition of the palladium metal in copper-based surfaces.The manufacturing cycle of alloy film is greatly shortened, the range of application of film has been widened, there is process is simple, reproducible, the preparation of suitable scale alloy film.
Description
Technical field
The present invention relates to a kind of plating technology of preparing of the controllable palladium-copper alloy film of component and thickness, the method is
Based on Pd2+And Cu2+Electronic reduction reaction principle is obtained in negative electrode, realizes that metal Pd and Cu are carried in porous ceramics
Reduction deposition film forming on body, two kinds of metals are layered alternatively plate, by the electric charge for controlling electrochemical reaction total
Amount, realizes the control to alloy film thickness and component, and then can prepare the controllable height of ideal thickness, component
The palladium-copper alloy film of performance.
Background technology
With developing rapidly for membrane separation technique, in various fields such as food, weaving, medicine, chemical industry,
It is widely applied.By taking the purifies and separates of hydrogen as an example, fine and close metal palladium membrane separation technique invests small,
Energy consumption is low, and stability is high, long service life, the purification H of high-efficiency environment friendly2.Will be exhausted in fossil energy,
Environmental pollution increasingly serious today, metal membrane separation technique has traditional transformation to separate irreplaceable excellent
Gesture.
Since the eighties in last century, research of the people to dense palladium film is increasingly ripe, traditional non-loading type palladium
Film, selectivity is high, and close to 100%, industrialized producing technology is perfect.But, in production process, to original
The purity requirement of material is high, and production cost is high, and Hydrogen Separation speed is low, at the same in the presence of storage and transport ask
Topic.Therefore, extensive industrial applications are not obtained.Afterwards, people concentrate on sight, load type gold
In the research of category palladium film.Compared to traditional mechanical press method, the non-loading type palladium film of preparation, with porous
Ceramics or porous stainless Steel material are the load type palladium film of carrier, on the one hand reduce the consumption of precious metals pd,
Industrial production cost is reduced, on the other hand, the loose structure of carrier is maintaining hydrogen choosing higher
While selecting property, H is reduced2Resistance to mass tranfer in Metal Palladium film, improves H2Infiltration rate and migration
Speed.
Support type dense palladium film system, in H2Separating-purifying field, shows：Low cost, high selectivity,
High yield and good mechanically and chemically stability.But, when reaction temperature T is less than 573K, reaction pressure
PH2During higher than 2.0MPa, the H dissolved in Pd films increases, and the phase transformation of membrane structure is caused, so as to easily produce
Raw Hydrogen Brittleness Phenomena.So as to greatly limit application of the Pd films under cryogenic high pressure.Correlative study shows, to palladium
A certain amount of Cu is mixed in film, the certain PdCu alloy films of component are formed, can significantly be widened, its is low
Range of application under temperature.The resistance to SO_2 of membrane material is improve simultaneously, the consumption of precious metals pd is reduced, and is reduced
Production cost.
Corresponding membrane material how is prepared, will be our problem demanding prompt solutions.Chemical vapor deposition (CVD)
With the method for physical vapour deposition (PVD) (PVD), it is necessary to the electronic equipment of costliness and heavy metal target source and organic
Metal precursor, in addition, reaction cavity needs the vacuum of superelevation, early stage equipment investment is very big.For
The development of new industry brings huge financial burden.And the chemical plating (ELP) based on self-catalyzed reaction
Method, the pattern strong adaptability of carrier simple with its equipment operation, reaction is gentle and be widely used in reality
The field such as test, produce, but being intended to obtain ideal thickness, the alloy film of accurate Pd, Cu composition but has certain
Difficulty.This is also a problem of load type palladium film research field.
The present invention, for problem present in the production of above-mentioned technology, with reference to the principle of plating film forming, according to life
The actual conditions of the membrane material needed for producing, build electrochemical system, using the technique of stepped depositions, by adjusting
Economize on electricity current density size, controls alloy film surface topography；Regulation often walks the quantity of electric charge of reaction, controls phase
The Pd of every layer for answering, Cu metal deposition capability.With reference to electroplating deposition number of metal, and then obtain component and thickness
Controllable palladium-copper alloy membrane material.
The content of the invention
To achieve the above object, the present invention provides the preparation of a kind of thickness and the controllable palladium-copper alloy film of component
Method and palladium-copper alloy film and application, the palladium-copper alloy film can suitable for Hydrogen Separation and purification process,
The environment of cryogenic high pressure.Specially using layering electric plating method, successively alternating deposit is golden on carrier to be plated
Category palladium and copper, control every layer of metal thickness and the amount of material respectively, and final high-temperature alloy forms fine and close
Palladium-copper alloy film.The method by the control to the system quantity of electric charge, so as to reach accurate deposition respective amount
Metal Palladium and copper, and then reach the purpose of the component of control alloy film.In addition, the method is by regulating and controlling electric current
Density, controls the quality of film, and the quantity of electric charge of adjustment and control system different phase controls the composition of palladium-copper alloy film,
And then reach regulation and control to alloy film thickness.
The palladium-copper alloy film prepared, with preferable low-temperature stability and resistance to SO_2, maintains higher
Low temperature hydrogen permeability, while the incorporation of copper is greatly reduced, the usage amount of heavy metal palladium, so as in certain journey
Production cost has been saved on degree.This high performance membrane material goes for, mixed under cryogenic high pressure environment
Close in gas, the use scope of traditional simple metal membrane material has been widened in efficiently separating and purification process for hydrogen.
The technical solution adopted in the present invention is：
Construction work electrode, to electrode and reference electrode three-electrode system, using the palladium ion in palladium plating solution and
Copper ion in copper electrolyte on the working electrode (s electron reduction principle on the working electrode (s electron reduction is
, on carrier, quantity of electric charge when being electroplated every time by regulation and control controls individual layer palladium film for palladium simple substance and copper simple substance electro-deposition
Or the thickness of copper film, multiple plated film, make palladium film or copper film layer by layer deposition, then by regulating and controlling during each plated film
The palladium-copper alloy film of different component and different-thickness is finally obtained to electrode and coating times, during palladium plating film
It is palladium electrode to electrode, during electroplating copper film is copper electrode to electrode.
During each plated film palladium film or copper film are controlled by regulating and controlling to set the compactness extent of current density control film forming
Quality.
The working electrode is porous ceramic pipe carrier material；The porous ceramic pipe carrier material is carried for ECN
Body or NJ carriers, with aluminum oxide as main component, the NJ is based on aluminum oxide and zirconium oxide for the ECN
Want composition；The working electrode is preceding in use, by pre-processing dust, oil to remove working electrode surface
Dirty and other impurities material.
In the composition of the palladium plating solution, main salt：[Pd(NH3)2]Cl2, auxiliary salt：NH4Cl, KCl, complexing agent：
25% NH4OH, free ammonia (NH3)；In the composition of copper electrolyte, main salt：EDTA-Cu, auxiliary salt：
KNO3, K4[Fe(CN)6]·H2O, brightener：2-2 bipyridyls (C10H8N2)。
[Pd(NH3)2]Cl2Mass concentration be 5g/L~10g/L, NH4The mass concentration of Cl is 5g/L~10g/L,
The mass concentration of KCl is 0.5g/L~2g/L, and complexing agent is 25% from 10mL/L~20ml/L mass fractions
NH4OH and 3g/L~6g/The free ammonia (NH3) of L；The mass concentration of EDTA-Cu is 10g/L~15g/L,
KNO3Mass concentration be 2g/L~5g/L, K4[Fe(CN)6]·H2The mass concentration of O is 1g/L~3g/L, 2-2
Bipyridyl (C10H8N2) it is 50mg/L；The pH of palladium plating solution is 8.0~9.5, and the pH of copper electrolyte is 8.5~10.0.
The temperature in use of palladium plating solution is 20 DEG C~50 DEG C, and the temperature in use of copper electrolyte is 35 DEG C~65 DEG C；
It is 20C to 80C, preferred scope 40C to 50C to be controlled during plated film per layer charge amount scope；
Current density control is in 0.05A/dm during plating palladium3~0.55A/dm3, sedimentation time is 10min to 20min,
Current density control is in 0.15A/dm during copper facing3~0.65A/dm3, sedimentation time is 15min to 30min.
On the working electrode (s during plated film, the first tunic is conductor of the palladium film as next step electroplating film；The thickness of film
Degree and quality can determine according to quality minusing.
Palladium-copper alloy film after the completion of preparation, under inert gas atmosphere, 500 DEG C~750 DEG C activation
500min~1000min.
The controllable palladium-copper alloy film of the component and thickness that are obtained according to above-mentioned preparation method.
The palladium-copper alloy film can be under cryogenic high pressure environment, the hydrogen for separating, purifying in mixed gas.
Compared to the method for traditional plated film, advantage of the invention is that：
1., by being layered electric plating method, realize to alloy film component, more accurately control.
2. control often walks the total amount of electric charge of reaction, realizes to palladium-copper alloy film thickness, more accurately control.
3. on working electrode, under the protection of electronics atmosphere, Pd2+Can directly in the deposition on Cu films surface,
Without destroying original copper film structure, traditional chemical plating is reduced, copper film needs answering for before palladium is plated alloying
Miscellaneous flow.
4. during electrochemical filming, the introducing of electric current, during instead of plated film, the work of reducing agent
With accelerating Pd2+, Cu2+The migration rate of ion, promotes reduction reaction of the ion in carrier surface, enters
And the reaction time is shortened, simplify technological process.
5. the present invention breaks through traditional chemical plating, and every layer of limitation for being required to alloying step breaches metal also
The limitation of former potential, realizes deposition of the palladium metal in copper-based surfaces.Substantially reduce the preparation week of alloy film
Phase, the range of application of film is widened, there is process is simple, reproducible, the conjunction of suitable scale
The preparation of golden film.
Brief description of the drawings
Fig. 1 is copper plating device schematic diagram.
Fig. 2 is plating palladium schematic device.
Fig. 3 electrode rotary schematic diagrames, wherein, W is working electrode, and C is that, to electrode, R is reference electrode.
Fig. 4 for alloy film material surface scan electron microscope wherein, (a) be ECN1 surface scan electron microscopes；
B () is NJ1 surface scan electron microscopes；C () is ECN2 surface scan electron microscopes；D () is NJ2 surface scans electricity
Mirror figure.
Fig. 5 is the XRD component analysis figures of alloy film.
Specific embodiment
The technology of the present invention details is subject to detailed description by following embodiments, and illustrated embodiment its effect is into one
Step explanation technical characteristic of the invention, it is of the invention rather than limiting.
The porous ceramic pipe carrier material is Dutch energy research institute production, with aluminum oxide as main component
, cellular ceramic substrate (ECN) or Nanjing University of Technology (thinking high-tech Co., Ltd in Nanjing nine) production,
With aluminum oxide and zirconium oxide as main component, cellular ceramic substrate (NJ).
1. when cellular ceramic substrate seed nucleus are pre-processed, imitate the carrier sensitization of traditional chemical plating and plant kernel mode, tool
Body is with reference to patent [Hou S F, Jiang K, Li W Z, Xu H Y, Yuan L X.A metal palladium
composite membrane or alloy palladium composite membrane and their
The A1 of preparation methods.WO 2005/065806], experimental principle and detailed protocol are not being repeated.
2. layer of metal deposition is often completed, distilled water need to be used, low-voltage vacuum washes membrane tube, except striping surface and load
The plating solution remained in body space, so that ensure that electroplates afterwards is smoothed out, while keeping the cleaning of membrane structure
It is smooth.
Technological process is as follows：
1. Vehicle element.
According to the porosity of carrier, surface apertures and modification Rotating fields, porous ceramic film material can be divided into ECN
Carrier and NJ carriers.
First, two kinds of carriers are intended to the alcohol solution for soaking 30min in sodium carbonate, remove the greasy dirt on surface.It
Afterwards, in deionized water, immersion washes 15min, removes the alkali alcosol of residual.Because ECN is carried
The decorative layer of body, main component is α-Al2O3；And the decorative layer of NJ carriers, main component is ZrO2, two
Person does not have electric conductivity, so to adhere to one layer of palladium core of electric conductivity in carrier surface in advance.Concrete operations
It is as follows：(can refer to patent Hou S F, Jiang K, Li W Z, Xu H Y, Yuan L X.A metal palladium
composite membrane or alloy palladium composite membrane and their
preparation methods.WO 2005/065806 A1).First it is the sensitization of carrier, porous stainless steel is carried
In body immersion dimethylamino monoborane, 3~5min is reduced；It is clean with distilled water flushing afterwards, immerse palladium sulfate
In the mixed liquor of borax, activation kind palladium core.Iterative cycles 3~5 times, until carrier film surface, color by
Untill white is changed into black gray expandable.So far, carrier conductive layer pretreatment is completed.
2. Cu electroplating.
Metal copper electrolyte is prepared, three-electrode electro Chemical system is built, suitable electrochemical parameter is adjusted.Such as Fig. 1,
Build reaction unit.Wherein, the carrier of pretreated conductive layer is working electrode；Copper pipe is to electrode, type
Number be red copper waveguide；Saturated calomel electrode is reference electrode, model (217).Regulation electrochemical parameter,
Select suitable operation interval.Scanning open-circuit voltage E firstO, it is determined that the upper voltage limit to be controlled.Afterwards,
Selection cyclic voltammetry (CV), the operating voltage interval Init needed for electrochemical reaction is set
E (- 0.65V~-0.90V), High E (- 0.65V~-0.90V), Low E (- 0.70V~-0.95V), Final
E (- 0.65V~-0.90V)；Sweep speed Scan Rate (0.01V/s~0.005V/s)；Scan period Sweep
Segments (200~2000)；Sensitivity S ensitivity (0.001A/V~0.0001A/V)；It is fixed according to Faraday
Rule：Q=zFn, (wherein Q is total quantity of electric charge, and z is the stoichiometric coefficient of electro transfer in electrochemical reaction,
The z=2 when copper participates in reacting；F is Faraday constants, about 96500C/mol；N is participation electrode reaction
Metal material amount), calculate and set, the quantity of electric charge Control-Run Status-About of required control
Experiment at Level Charge(C).Finally, start magnetic force heating stirrer and electrochemical workstation, open
Beginning copper facing is tested, and according to the quantity of electric charge C for setting before, is converted into the quality m of metal copper coatingCuAnd thickness
dCu.Every layer of Cu thickness of general control is no more than 0.5 μm.
3. electrochemical plating palladium.
Metal palladium plating solution is prepared, three-electrode electro Chemical system is built, suitable electrochemical parameter is adjusted.Such as Fig. 2,
Build reaction unit.Wherein, the carrier of pretreated conductive layer is working electrode；Platinum electrode be to electrode,
Model (Pt005)；Saturated calomel electrode is reference electrode, model (217).Regulation electrochemical parameter, choosing
Select suitable operation interval.Scanning open-circuit voltage E firstO, it is determined that the upper voltage limit to be controlled.Afterwards,
Selection cyclic voltammetry (CV), the operating voltage interval Init needed for electrochemical reaction is set
E (- 0.60V~-0.90V), High E (- 0.60V~-0.90V), Low E (- 0.65V~-0.95V), Final
E (- 0.60V~-0.90V)；Sweep speed Scan Rate (0.01V/s~0.005V/s)；Scan period Sweep
Segments (200~2000)；Sensitivity S ensitivity (0.001A/V~0.0001A/V)；It is fixed according to Faraday
Rule：Q=zFn, (wherein Q is total quantity of electric charge, and z is the stoichiometric coefficient of electro transfer in electrochemical reaction,
The z=2 when palladium participates in reacting；F is Faraday constants, about 96500C/mol；N is participation electrode reaction
Metal material amount), calculate and set, the quantity of electric charge Control-Run Status-About of required control
Experiment at LevelFinally, start magnetic force heating stirrer and electrochemical workstation, open
Begin to plate palladium experiment, according to the quantity of electric charge C for setting before, be converted into the quality m of Metal Palladium coatingPdAnd thickness
dPd.Every layer of Pd thickness of general control is no more than 0.5 μm.
4. circulation 2,3 is operated, and according to needs of production, prepares different component, the palladium-copper alloy film of different-thickness
Material.
5. in tube furnace N2Alloying under atmosphere, ensures the excellent of alloy film properties.
Embodiment 1
ECN1 porous ceramic film materials are carrier, the Pd of 4 μ m-thicks50Cu50The preparation of alloy film
1. the preparation of copper electrolyte
HFA2004 assay balances are used, 30gNa is weighed2EDTA is dissolved in the warm water of 40 DEG C -50 DEG C of 400ml,
It is designated as solution A standby.Weigh 10g CuSO4·5H2O is dissolved in the warm water of 40 DEG C of 100ml, is designated as
solution B.A is lentamente stirred down and is added in B, in blue-tinted transparent solution, produce blue precipitate,
Become cloudy.Reaction equation is：
Cu2++2OH-→Cu(OH)2↓Cu2++Na2EDTA→CuEDTA+2Na+
Cu(OH)2+Na2EDTA→CuEDTA+2NaOH
Weigh 23g Na2CO3It is dissolved in the warm water of 40 DEG C of 100ml.Solution C are designated as, C are slowly stirred and are added
Enter in B, the blue precipitate for previously having produced fades away, and solution becomes clarification again.Ultrasonic 5min, makes molten
Liquid mixing is more uniform.Weigh 40mg C10H8O2It is dissolved in 40ml distilled water, is designated as solution D, claims
Take 60mgK4[Fe(CN)6]·3H2O is dissolved in 50ml distilled water, is designated as solution E, under stirring, slowly
D, E are added in B, 1L is settled to, pH to 9.0~10.0 is adjusted.So far, blue-tinted transparent is obtained
Copper electrolyte.
2. the preparation of palladium plating solution
1.7g PdCl are weighed with HFA2004 assay balances2, it is dissolved in the HCl of 65 DEG C 10% of 3mL, generate
Peony H2PdCl4Solution.Reaction equation is:
PdCl2After being completely dissolved, 3mL~5mL relative densities are slowly added under stirring for 0.89g/cm3's
NH3H2O, with the dark red solution pink gelatinous precipitate of reaction generation, adds excess of ammonia water, until raw
Into red precipitate be completely dissolved, and generate the [Pd (NH of grass green3)4]Cl2Untill solution.Reaction equation is：
H2PdCl4+6NH4OH→[Pd(NH3)4]Cl2+2NH4Cl+6H2O
Undesired impurities are filtered off, the HCl of 40mL-50mL10% is slowly added in clear liquid, until in solution completely
It is settled out glassy yellow [Pd (NH3)2]Cl2Untill precipitation.Precipitated with the Buchner funnel suction filtration that depressurizes, and with distilled water pair
Precipitation cleaning, untill the thick precipitation of glassy yellow is formed.By suction filtration and the [Pd (NH that clean up3)2]Cl2
50mL relative densities are dissolved in for 0.89g/cm3NH3H2In O, the NH of the 1mol/L for preparing in advance is added4Cl
Solution regulation system pH to 8.5-9.5, that is, obtain micro- green transparent palladium plating solution.
3. Vehicle element
ECN cellular ceramic substrates pipe range 67.75mm, external diameter 14.05mm, internal diameter 10.95mm.Exist first
Na2CO3Alcohol solution for soaking 30min, remove surface greasy dirt.Soak in deionized water afterwards, it is low
Pressure vacuum washes 15min, removes the Na of residual2CO3Alcoholic solution, after treatment, the pure white light of carrier.It
Afterwards, 150 DEG C of dry for standby in an oven.
Carrier to drying and processing is activated, and in immersion reducing agent (dimethylamino monoborane), reduces 3~5min,
Support tube is rinsed well with distilled water, is immersed afterwards in the mixed liquor of palladium sulfate and borax, activation kind Pd cores.
Iterative cycles 3~5 times, until carrier surface, untill color is changed into black gray expandable from white.
4. Cu electroplating
Such as Fig. 1, reaction unit is built, working electrode is connected, to electrode and reference electrode.First, scanning is opened
Road voltage EO, it is determined that the upper voltage limit E to be controlledMax=-0.915V.Afterwards, selection cyclic voltammetry (CV),
Relevant parameter (High E=-0.65V~-0.75V, Low E=-0.75V~-0.85V is set；Scan Rate=0.01V/s
Sweep Segments=1000；Sensitivity=0.001A/V).The total amount of electric charge Q=35.89C of copper plate is set
It is 0.25A/dm to control work volume current density3~0.45A/dm3, current efficiency is 90%.After 10min, obtain
To the copper film that surface-brightening is brick-red.
5. electrochemical plating palladium
Such as Fig. 2, reaction unit, connection electrode are built.First, scanning open-circuit voltage EO, it is determined that to be controlled
The upper voltage limit E of systemMax=-0.885V.Afterwards, selection cyclic voltammetry (CV), sets relevant parameter (High
E=-0.65V~-0.75V, Low E=-0.75V~-0.85V；Scan Rate=0.01V/s；Sweep
Segments=1000；Sensitivity=0.001A/V).The quantity of electric charge Q=28.82C of plating palladium layers is set.Control
Volume current density is 0.15A/dm3~0.45A/dm3, current efficiency is 90%.After 8min, surface-brightening is obtained
Palladium film with silvery white metallic luster.
6. circulation plating prepares alloy film
4.5 liang of steps are repeated, realizes that Cu-Pd-Cu-Pd metal levels alternately increase.Finally add up plating Cu 5
Layer, 5 layers of Pd.Every layer of about 0.4 μm, totally 4 μm of metal layer thickness.The alloy film for completing will be prepared, in pipe
N in formula stove2Alloying 1000min under atmosphere.
After the completion of alloying, to the appearance structure of palladium-copper alloy film, carry out SEM signs (shown in such as Fig. 4 (a)).With
Stainless steel end socket, after being encapsulated with reference to graphite ferrule, measures the saturating nitrogen quantity of 0.1MPa under the normal temperature of the alloy film：
FN2=0.08ml/min, selectivity：H/N=1356.
Embodiment 2
NJ1 porous ceramic film materials are carrier, the Pd of 4 μ m-thicks47Cu53The preparation of alloy film
1. the preparation of copper electrolyte
Method is with embodiment 2.
2. the preparation of palladium plating solution
Method is with embodiment 2.
3. Vehicle element
NJ cellular ceramic substrates pipe range 67.90mm, external diameter 12.50mm, internal diameter 8.05mm.First in Na2CO3
Alcohol solution for soaking 30min, remove surface greasy dirt.Soak in deionized water afterwards, low-voltage vacuum is taken out
15min is washed, the Na of residual is removed2CO3Alcoholic solution, after treatment, the pure white light of carrier.Afterwards, drying
150 DEG C of dry for standby in case,
Carrier to drying and processing is activated, and in immersion reducing agent (dimethylamino monoborane), reduces 3~5min,
Support tube is rinsed well with distilled water, is immersed afterwards in the mixed liquor of palladium sulfate and borax, activation kind Pd cores.
Iterative cycles 3~5 times, until carrier surface, untill color is changed into black gray expandable from white.
4. Cu electroplating
Such as Fig. 1, reaction unit is built, working electrode is connected, to electrode and reference electrode.First, scanning is opened
Road voltage EO, it is determined that the upper voltage limit E to be controlledMax=-0.952V.Afterwards, selection cyclic voltammetry (CV),
Relevant parameter (High E=-0.65V~-0.75V, Low E=-0.75V~-0.85V is set；Scan Rate=0.01V/s；
Sweep Segments=1000；Sensitivity=0.001A/V).The total amount of electric charge of copper plate is set
Q=32.11C.It is 0.25A/dm to control working current density3~0.55A/dm3, current efficiency is 90%.8min
Afterwards, the brick-red copper film of surface-brightening is obtained.
5. electrochemical plating palladium
Such as Fig. 2, reaction unit, connection electrode are built.First, scanning open-circuit voltage EO, it is determined that to be controlled
The upper voltage limit E of systemMax=-0.907V.Afterwards, selection cyclic voltammetry (CV), sets relevant parameter (High
E=-0.65V~-0.75V, Low E=-0.75V~-0.85V；Scan Rate=0.01V/s；Sweep
Segments=1000；Sensitivity=0.001A/V).The quantity of electric charge Q=25.79C of plating palladium layers is set.Control
Current density is 0.15A/dm3~0.45A/dm3, current efficiency is 90%.After 5min, surface-brightening tool is obtained
There is the palladium film of silvery white metallic luster.
6. circulation plating prepares alloy film
4.5 liang of steps are repeated, realizes that Cu-Pd-Cu-Pd metal levels alternately increase.Finally add up plating Cu 5
Layer, 5 layers of Pd.Every layer of about 0.4 μm, totally 4 μm of metal layer thickness.The alloy film for completing will be prepared, in pipe
N in formula stove2Alloying 1000min under atmosphere.
After the completion of alloying, to the appearance structure of palladium-copper alloy film, carry out SEM signs (shown in such as Fig. 4 (b)).
Stainless steel end socket is used, after being encapsulated with reference to graphite ferrule, the saturating nitrogen quantity of 0.1MPa under the normal temperature of the alloy film is measured：
FN2=0.15ml/min, selectivity：H/N=1869.
Embodiment 3
ECN2 porous ceramic film materials are carrier, the Pd of 5 μ m-thicks45Cu55The preparation of alloy film
1. the preparation of copper electrolyte
Method is with embodiment 2.
2. the preparation of palladium plating solution
Method is with embodiment 2.
3. Vehicle element
ECN cellular ceramic substrates pipe range 80.25mm, external diameter 14.00mm, internal diameter 11.05mm.Exist first
Na2CO3Alcohol solution for soaking 30min, remove surface greasy dirt.Soak in deionized water afterwards, it is low
Pressure vacuum washes 15min, removes the Na of residual2CO3Alcoholic solution, after treatment, the pure white light of carrier.It
Afterwards, 150 DEG C of dry for standby in an oven,
Carrier to drying and processing is activated, and in immersion reducing agent (dimethylamino monoborane), reduces 3~5min,
Support tube is rinsed well with distilled water, is immersed afterwards in the mixed liquor of palladium sulfate and borax, activation kind Pd cores.
Iterative cycles 3~5 times, until carrier surface, untill color is changed into black gray expandable from white.
4. Cu electroplating
Such as Fig. 1, reaction unit is built, working electrode is connected, to electrode and reference electrode.First, scanning is opened
Road voltage EO, it is determined that the upper voltage limit E to be controlledMax=-0.974V.Afterwards, selection cyclic voltammetry (CV),
Relevant parameter (High E=-0.65V~-0.75V, Low E=-0.75V~-0.85V is set；Scan Rate=0.01V/s；
Sweep Segments=1000；Sensitivity=0.001A/V).The total amount of electric charge of copper plate is set
Q=53.51C.It is 0.25A/dm to control working current density3~0.55A/dm3, current efficiency is 90%.10min
Afterwards, the brick-red copper film of surface-brightening is obtained.
5. electrochemical plating palladium
Such as Fig. 2, reaction unit, connection electrode are built.First, scanning open-circuit voltage EO, it is determined that to be controlled
The upper voltage limit E of systemMax=-0.901V.Afterwards, selection cyclic voltammetry (CV), sets relevant parameter (High
E=-0.65V~-0.75V, Low E=-0.75V~-0.85V；Scan Rate=0.01V/s；Sweep
Segments=1000；Sensitivity=0.001A/V).The quantity of electric charge Q=42.98C of plating palladium layers is set.Control
Current density is 0.15A/dm3~0.45A/dm3, current efficiency is 90%.After 8min, surface-brightening tool is obtained
There is the palladium film of silvery white metallic luster.
6. circulation plating prepares alloy film
4.5 liang of steps are repeated, realizes that Cu-Pd-Cu-Pd metal levels alternately increase.Finally add up plating Cu 5
Layer, 5 layers of Pd.Every layer of about 0.5 μm, totally 5.0 μm of metal layer thickness.The alloy film for completing will be prepared,
N in tube furnace2Alloying 1000min under atmosphere
After the completion of alloying, to the appearance structure of palladium-copper alloy film, carry out SEM signs (shown in such as Fig. 4 (c)).With
Stainless steel end socket, after being encapsulated with reference to graphite ferrule, measures the saturating nitrogen quantity of 0.1MPa under the normal temperature of the alloy film：
FN2=0.05ml/min, selectivity：H/N=1015.
Embodiment 4
NJ2 porous ceramic film materials are carrier, the Pd of 5 μ m-thicks40Cu60The preparation of alloy film
1. the preparation of copper electrolyte
Method is with embodiment 2.
2. the preparation of palladium plating solution
Method is with embodiment 2.
3. Vehicle element
NJ cellular ceramic substrates pipe range 70.55mm, external diameter 12.70mm, internal diameter 8.15mm.First in Na2CO3
Alcohol solution for soaking 30min, remove surface greasy dirt.Soak in deionized water afterwards, low-voltage vacuum is taken out
15min is washed, the Na of residual is removed2CO3Alcoholic solution, after treatment, the pure white light of carrier.Afterwards, drying
150 DEG C of dry for standby in case,
Carrier to drying and processing is activated, and in immersion reducing agent (dimethylamino monoborane), reduces 3~5min,
Support tube is rinsed well with distilled water, is immersed afterwards in the mixed liquor of palladium sulfate and borax, activation kind Pd cores.
Iterative cycles 3~5 times, until carrier surface, untill color is changed into black gray expandable from white.
4. Cu electroplating
Such as Fig. 1, reaction unit is built, working electrode is connected, to electrode and reference electrode.First, scanning open circuit electricity
Pressure EO, it is determined that the upper voltage limit E to be controlledMax=-0.933V.Afterwards, selection cyclic voltammetry (CV),
Relevant parameter (High E=-0.65V~-0.75V, Low E=-0.75V~-0.85V is set；Scan Rate=0.01V/s；
Sweep Segments=1000；Sensitivity=0.001A/V).The total amount of electric charge of copper plate is set
Q=42.38C.It is 0.25A/dm to control working current density3~0.55A/dm3, current efficiency is 90%.8min
Afterwards, the brick-red copper film of surface-brightening is obtained.
5. electrochemical plating palladium
Such as Fig. 2, reaction unit, connection electrode are built.First, scanning open-circuit voltage EO, it is determined that to be controlled
The upper voltage limit E of systemMax=-0.861V.Afterwards, selection cyclic voltammetry (CV), sets relevant parameter (High
E=-0.65V~-0.75V, Low E=-0.75V~-0.85V；Scan Rate=0.01V/s；Sweep
Segments=1000；Sensitivity=0.001A/V).The quantity of electric charge Q=34.03C of plating palladium layers is set.Control
Current density is 0.15A/dm3~0.45A/dm3, current efficiency is 90%.After 5min, surface-brightening tool is obtained
There is the palladium film of silvery white metallic luster.
6. circulation plating prepares alloy film
4.5 liang of steps are repeated, realizes that Cu-Pd-Cu-Pd metal levels alternately increase.Finally add up plating Cu 5
Layer, 5 layers of Pd.Every layer of about 0.5 μm, totally 5 μm of metal layer thickness.The alloy film for completing will be prepared, in pipe
N in formula stove2Alloying 1000min under atmosphere.
After the completion of alloying, to the appearance structure of palladium-copper alloy film, carry out SEM signs (shown in such as Fig. 4 (d)).
Stainless steel end socket is used, after being encapsulated with reference to graphite ferrule, the saturating nitrogen quantity of 0.1MPa under the normal temperature of the alloy film is measured：
FN2=0.1ml/min, selectivity：H/N=1516.
Claims (10)
1. the preparation method of a kind of component and the controllable palladium-copper alloy film of thickness, it is characterised in that：Construction work electricity
Pole, to electrode and reference electrode three-electrode system, using the copper in the palladium ion and copper electrolyte in palladium plating solution from
The principle that son obtains electron reduction on the working electrode (s obtains electron reduction for palladium simple substance and copper simple substance on the working electrode (s
In on carrier, quantity of electric charge when being electroplated every time by regulation and control controls the thickness of individual layer palladium film or copper film for electro-deposition,
Multiple plated film, makes palladium film or copper film layer by layer deposition, then secondary to electrode and plated film during each plated film by regulating and controlling
Number finally obtains the palladium-copper alloy film of different component and different-thickness, and during palladium plating film is palladium electrode to electrode,
During electroplating copper film is copper electrode to electrode.
2. preparation method according to claim 1, it is characterised in that：By regulating and controlling to set during each plated film
The compactness extent of current density control film forming controls the quality of palladium film or copper film.
3. preparation method according to claim 1, it is characterised in that：The working electrode is porous ceramics
Pipe carrier material, the porous ceramic pipe carrier material is ECN carriers or NJ carriers；The working electrode
It is preceding using, by pre-processing dust, greasy dirt and other impurities material to remove working electrode surface.
4. preparation method according to claim 1, it is characterised in that：It is main in the composition of the palladium plating solution
Salt：[Pd(NH3)2]Cl2, auxiliary salt：NH4Cl, KCl, complexing agent：25% NH4OH, free ammonia (NH3)；
In the composition of copper electrolyte, main salt：EDTA-Cu, auxiliary salt：KNO3, K4[Fe(CN)6]·H2O, brightener：
2-2 bipyridyls (C10H8N2)。
5. preparation method according to claim 4, it is characterised in that：[Pd(NH3)2]Cl2Mass concentration
It is 5g/L~10g/L, NH4The mass concentration of Cl is 5g/L~10g/The mass concentration of L, KCl is 0.5g/L~2g/L,
Complexing agent is from the NH that 10mL/L~20ml/L mass fractions are 25%4OH and 3g/L~6g/L's is free
Ammonia (NH3)；The mass concentration of EDTA-Cu is 10g/L~15g/L, KNO3Mass concentration be
2g/L~5g/L, K4[Fe(CN)6]·H2The mass concentration of O is 1g/L~3g/L, 2-2 bipyridyls (C10H8N2)
It is 50mg/L；The pH of palladium plating solution is 8.0~9.5, and the pH of copper electrolyte is 8.5~10.0.
6. preparation method according to claim 1, it is characterised in that：The temperature in use of palladium plating solution is
20 DEG C~50 DEG C, the temperature in use of copper electrolyte is 35 DEG C~65 DEG C；
It is 20C to 80C, preferred scope 40C to 50C to be controlled during plated film per layer charge amount scope；
Current density control is in 0.05A/dm during plating palladium3~0.55A/dm3, sedimentation time is 10min to 20min,
Current density control is in 0.15A/dm during copper facing3~0.65A/dm3, sedimentation time is 15min to 30min.
7. preparation method of the claim according to 1, it is characterised in that：On the working electrode (s during plated film, the
One tunic is conductor of the palladium film as next step electroplating film；The thickness and quality of film can be true according to quality minusing
It is fixed.
8. preparation method according to claim 1, it is characterised in that：Palladium-copper alloy film after the completion of preparation,
Under inert gas atmosphere, 500 DEG C~750 DEG C activation 500min~1000min.
9. a kind of component obtained according to any preparation methods of claim 1-8 and the controllable palladium copper of thickness are closed
Golden film.
10. palladium-copper alloy film described in a kind of claim 9 is separated, purifies gaseous mixture under cryogenic high pressure environment
The application of the hydrogen in body.
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| CN108624923A (en) * | 2018-06-21 | 2018-10-09 | 深圳市西凡谨顿科技有限公司 | Electroforming thickness of coating automatic control device and system |
| CN109137021A (en) * | 2018-09-19 | 2019-01-04 | 江西华度电子新材料有限公司 | A kind of preparation method of hot plate liquid-sucking core |
| CN109137020A (en) * | 2018-09-19 | 2019-01-04 | 江西华度电子新材料有限公司 | A kind of preparation method of thickness liquid-sucking core |
| CN109837562A (en) * | 2017-11-24 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of method that chemical plating/plating prepares palladium tube |
| CN109876745A (en) * | 2017-12-06 | 2019-06-14 | 中国科学院大连化学物理研究所 | The palladium copper composite film material of load TS -1 molecular sieve and preparation and application |
| CN110903265A (en) * | 2018-09-14 | 2020-03-24 | 中国科学院大连化学物理研究所 | Method for carrying out gas phase propylene epoxidation reaction in palladium membrane reactor |
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| CN109876745A (en) * | 2017-12-06 | 2019-06-14 | 中国科学院大连化学物理研究所 | The palladium copper composite film material of load TS -1 molecular sieve and preparation and application |
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| CN110903265A (en) * | 2018-09-14 | 2020-03-24 | 中国科学院大连化学物理研究所 | Method for carrying out gas phase propylene epoxidation reaction in palladium membrane reactor |
| CN109137021A (en) * | 2018-09-19 | 2019-01-04 | 江西华度电子新材料有限公司 | A kind of preparation method of hot plate liquid-sucking core |
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| CN111992048A (en) * | 2020-07-29 | 2020-11-27 | 苏州高迈新能源有限公司 | Preparation method of alloy palladium membrane |
| CN115689063A (en) * | 2022-12-30 | 2023-02-03 | 工业富联(杭州)数据科技有限公司 | Gold film thickness prediction method and device, electronic device and storage medium |
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