CN109097800A - A method of metal rhodium or rhodium alloy are prepared by electro-deposition or chemical deposition - Google Patents
A method of metal rhodium or rhodium alloy are prepared by electro-deposition or chemical deposition Download PDFInfo
- Publication number
- CN109097800A CN109097800A CN201811154290.XA CN201811154290A CN109097800A CN 109097800 A CN109097800 A CN 109097800A CN 201811154290 A CN201811154290 A CN 201811154290A CN 109097800 A CN109097800 A CN 109097800A
- Authority
- CN
- China
- Prior art keywords
- rhodium
- solution
- ion
- metal
- alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
-
- 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
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals 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
- C23C18/48—Coating with alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/24—Alloys obtained by cathodic reduction of all their ions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
Abstract
A method of metal rhodium or rhodium alloy being prepared by electro-deposition or chemical deposition, the preparation method includes electrodeposition process and chemical deposition, and the plating solution is faintly acid or alkali plating solution.The preparation step of metal rhodium or rhodium alloy are as follows: (1) composition according to patent CN105906668B prepares the complex solution of rhodium with method；(2) complex solution of dissimilar metal ion is prepared；(3) mixed solution containing reducing agent and additive is prepared；(4) (1), (2), (3) acquired solution are mixed according to demand in proportion and adjusts pH with ammonium hydroxide and acid solution；(5) rhodium or rhodium alloy coating are prepared using electrodeposition process or chemical deposition.The present invention uses faintly acid or alkaline solution system, avoid the displacement reaction in highly acid plating solution, binding force of cladding material is good, improve that current efficiency caused by a large amount of liberations of hydrogen of highly acid system is low and the high problem of porosity, using improved complexing agent and additive is introduced, improves the stability of alkali plating solution.
Description
Technical field
The invention belongs to field of alloy preparation technology, and in particular to one kind prepares metal by electro-deposition or chemical deposition
The method of rhodium or rhodium alloy.
Background technique
Metal rhodium chemical stability is high, does not dissolve in general bronsted lowry acids and bases bronsted lowry, is only very slightly soluble in chloroazotic acid, anti-Atmospheric Sulfur compound and two
The corrosivity of the gases such as carbonoxide is strong, and since its own is with gloss, rhodium coating is in anti-silver tarnish coating and decoration
Property plating in have a wide range of applications.In addition, metal rhodium hardness is high, contact resistance is small, good conductivity, can be used in electronics finishing
In the overlay coating of plugging member, HF switch etc., to improve contact reliability.In catalytic field, metal rhodium is also that one kind has both
The catalyst of higher catalytic activity and stability, but since rhodium price is higher, using the alloy of base metal and rhodium as catalyst
Have become research hotspot.
Compared to preparation methods such as Vacuum Deposition, chemical vapor depositions, electro-deposition and chemical deposition prepare metal and its conjunction
Gold plate has many advantages, such as at low cost, and operating procedure is simple, and chemical deposition also has and do not influenced by current distribution, can obtain
Homogeneous coating and be suitable for various matrixes, including metal, semiconductor and nonmetallic outstanding advantage.
Currently, having prepared the technique of rhodium coating in strongly acidic solution (sulfuric acid, phosphoric acid, sulfamic acid) by electrodeposition process
Have been reported that, however, due in highly acid system cathode surface liberation of hydrogen it is serious, in strongly acidic solution electro-deposition rhodium electric current effect
Rate only has 40% ~ 60%, and evolving hydrogen reaction also easily leads to plating layer porosity and increases；Chemical deposition prepares rhodium coating and is common in faintly acid
And in alkaline solution, but reported technique, mostly using ammonium hydroxide as complexing agent, ammonium hydroxide complexing power is limited, and bath stability is poor.?
The complexing agent of trivalent rhodium and its preparation method of complex compound, available alkalinity are disclosed in the patent CN105906668B of authorization
Stable complex compound in solution.
Summary of the invention
The purpose of the present invention is to solve the existing rhodium plating problems that layer porosity is larger, bath stability is poor, provide
A method of metal rhodium or rhodium alloy are prepared by electro-deposition or chemical deposition.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A method of metal rhodium or rhodium alloy being prepared by electrodeposition process, specific step is as follows for the method:
(1) complex solution for preparing rhodium ion, is denoted as solution A；
(2) complex solution for preparing the dissimilar metal ion that dissimilar metal ion concentration is 2 mol/L, is denoted as B solution；
(3) solution A is mixed into (being the plating solution of electro-deposition monometallic rhodium when B solution is 0) by the volume ratio of 1:0 ~ 10 with B solution,
PH value is adjusted to 5.5 ~ 12 with ammonium hydroxide and acid solution；
(4) matrix Jing Guo pre-treatment is placed in the solution of step (3) preparation, connects power cathode as cathode, separately takes one
Insoluble anode connects positive pole as anode, adjusts electro-deposition process parameter, obtains metal rhodium after 2 ~ 20 min of electro-deposition
Or rhodium alloy；The electro-deposition process parameter includes current waveform and current density, temperature, mixing speed, current waveform packet
Square wave, half-sinusoid, sawtooth wave are included, current density range is 0.5 ~ 3 A/dm2, temperature be 20 ~ 80 DEG C, mixing speed be 0 ~
1000 revs/min.
A method of metal rhodium or rhodium alloy being prepared by chemical deposition, specific step is as follows for the method:
(1) complex solution for preparing rhodium ion, is denoted as solution A；
(2) complex solution for preparing the dissimilar metal ion that dissimilar metal ion concentration is 2 mol/L, is denoted as B solution；
(3) aqueous solution for containing 0.2 ~ 20 g/L reducing agent and 0.1 ~ 200 mg/L additive is prepared, C solution is denoted as；
(4) tri- kinds of solution of A, B, C are mixed by the volume ratio of 1:0 ~ 10:1 ~ 10, is adjusted pH value to 5.5 with ammonium hydroxide and acid solution
~12；
(5) metal, semiconductor or the nonmetal basal body after the metallic matrix with catalytic activity or activation processing are placed in step
(4) in the solution prepared, adjusting process parameter, after 10 ~ 60 min of chemical deposition, i.e., matrix surface obtain corresponding rhodium layer or
Rhodium alloy layer；The technological parameter refers to temperature and mixing speed, and temperature range is 50 ~ 80 DEG C, mixing speed is 0 ~ 500 turn/
Minute.
The beneficial effect of the present invention compared with the existing technology is: electro-deposition or chemistry are carried out in faintly acid or alkaline solution
Deposition, avoids displacement reaction of the metallic matrix in strongly acidic solution, and binding force of cladding material is good；Higher pH value inhibits analysis
The current efficiency of hydrogen side reaction, electrodeposition process is high (> 70%), and plating layer porosity is small；Using the network in patent CN105906668B
Mixture and method prepare the complex compound of rhodium, and bath stability is long placed in and does not hydrolyze；For additive to be added in the plating solution of chemical deposition,
Bath stability is high.
Detailed description of the invention
Fig. 1 is the energy spectrum diagram of the rhodium coating of DC electrodeposition preparation on red copper matrix；
Fig. 2 is the energy spectrum diagram of the rhodium coating of pulse electrodeposition preparation on nickel coating；
Fig. 3 is the energy spectrum diagram of the rhodium layer prepared on chemical Ni-plating layer using hydrazine as reducing agent；
The energy spectrum diagram for the nickel rhodium that Fig. 4 is prepared when being using dimethylamino borine and sodium hypophosphite as reducing agent.
Specific embodiment
Further description of the technical solution of the present invention with reference to the accompanying drawings and examples, and however, it is not limited to this,
It is all that modifying or equivalently replacing the technical solution of the present invention, without departing from the spirit and scope of the technical solution of the present invention,
It should all cover within the protection scope of the present invention.
Specific embodiment 1: what present embodiment recorded is a kind of to prepare metal rhodium or rhodium alloy by electrodeposition process
Method, specific step is as follows for the method:
(1) by method described in patent CN105906668B, rhodium salt is dissolved in an acidic solution, by complexing agent in alkaline solution
The pH value of solution after mixing the two, is gradually adjusted to 5 ~ 12 under heating and stirring condition, obtains rhodium ion by middle dissolution
Complex solution is denoted as solution A；
(2) complex solution for preparing the dissimilar metal ion that dissimilar metal ion concentration is 2 mol/L, is denoted as B solution；
(3) solution A is mixed into (being the plating solution of electro-deposition monometallic rhodium when B solution is 0) by the volume ratio of 1:0 ~ 10 with B solution,
PH value is adjusted to 5.5 ~ 12 with ammonium hydroxide and acid solution；
(4) matrix Jing Guo pre-treatment is placed in the solution of step (3) preparation, connects power cathode as cathode, separately takes one
Insoluble anode (such as DSA anode, graphite anode, stainless steel anode or anode of lead dioxide) connects positive pole as anode,
Electro-deposition process parameter is adjusted, obtains metal rhodium or rhodium alloy after 2 ~ 20 min of electro-deposition；The electro-deposition process parameter packet
Current waveform and current density, temperature, mixing speed are included, current waveform includes square wave, half-sinusoid, sawtooth wave, current density
Range is 0.5 ~ 3 A/dm2, temperature is 20 ~ 80 DEG C, and mixing speed is 0 ~ 1000 rev/min.
Specific embodiment 2: one kind described in specific embodiment one prepares metal rhodium or rhodium alloy by electrodeposition process
Method, the electrodeposition process includes DC electrodeposition and pulse electrodeposition.
Specific embodiment 3: one kind described in specific embodiment one prepares metal rhodium or rhodium alloy by electrodeposition process
Method, in step (1), the concentration of rhodium ion is 0.1 ~ 10 g/L in the complex solution of the rhodium ion；The rhodium from
Son is provided by one or more of rhodium sulfate, phosphoric acid rhodium, radium chloride, iodate rhodium, rhodium nitrate, chlorine rhodate, preferably sulfuric acid
Rhodium, radium chloride or chlorine rhodium acid.
Specific embodiment 4: one kind described in specific embodiment one prepares metal rhodium or rhodium alloy by electrodeposition process
Method, in step (2), the dissimilar metal ion is one of copper, nickel, zinc, cobalt, iron, chromium, iridium, ruthenium, palladium, gold, silver
Or it is several, and corresponding complex compound is prepared using complexing agent described in CN105906668B.
Specific embodiment 5: one kind described in specific embodiment one prepares metal rhodium or rhodium alloy by electrodeposition process
Method, in step (3), the acid solution is one of sulfuric acid solution, hydrochloric acid solution or phosphoric acid solution；The matrix
For metal or electrically conductive, non-metallic material.
Specific embodiment 6: what present embodiment recorded is that one kind by chemical deposition prepares metal rhodium or rhodium alloy
Method, specific step is as follows for the method:
(1) by method described in patent CN105906668B, rhodium salt is dissolved in an acidic solution, by complexing agent in alkaline solution
The pH value of solution after mixing the two, is gradually adjusted to 5 ~ 12 under heating and stirring condition, obtains rhodium ion by middle dissolution
Complex solution is denoted as solution A；
(2) complex solution for preparing the dissimilar metal ion that dissimilar metal ion concentration is 2 mol/L, is denoted as B solution；
(3) aqueous solution for containing 0.2 ~ 20 g/L reducing agent and 0.1 ~ 200 mg/L additive is prepared, C solution is denoted as；
(4) tri- kinds of solution of A, B, C are mixed by the volume ratio of 1:0 ~ 10:1 ~ 10, is adjusted pH value to 5.5 with ammonium hydroxide and acid solution
~12；
(5) metal, semiconductor or the nonmetal basal body after the metallic matrix with catalytic activity or activation processing are placed in step
(4) in the solution prepared, adjusting process parameter, after 10 ~ 60 min of chemical deposition, i.e., matrix surface obtain corresponding rhodium layer or
Rhodium alloy layer；The technological parameter refers to temperature and mixing speed, and temperature range is 50 ~ 80 degrees Celsius, mixing speed is 0 ~
500 revs/min.
Specific embodiment 7: one kind described in specific embodiment six prepares metal rhodium by chemical deposition or rhodium closes
The method of gold, in step (1), 0.1 ~ 10 g/L of concentration of rhodium ion in the complex solution of the rhodium ion；The rhodium from
Son is provided by one or more of rhodium sulfate, phosphoric acid rhodium, radium chloride, iodate rhodium, rhodium nitrate, chlorine rhodate, preferably sulfuric acid
Rhodium, radium chloride or chlorine rhodium acid.
Specific embodiment 8: one kind described in specific embodiment six prepares metal rhodium by chemical deposition or rhodium closes
The method of gold, in step (2), the dissimilar metal ion is one or more of nickel, cobalt, palladium, gold, copper, ruthenium, silver.
Specific embodiment 9: one kind described in specific embodiment six prepares metal rhodium by chemical deposition or rhodium closes
The method of gold, in step (3), the reducing agent be amino borane, hydrazine, sodium borohydride, sodium hypophosphite, formaldehyde, in glyoxalic acid
One kind and a variety of mixtures；The additive is thiocarbamide, lead ion, UPS, Potassiumiodate, potassium iodide, saccharin, iron cyaniding
The mixture of one or more of potassium, potassium ferrocyanide, potassium rhodanide, dodecyl sodium sulfate and PEG；The acid solution
For one of sulfuric acid solution, hydrochloric acid solution or phosphoric acid solution；The matrix is metal, one in nonmetallic or semiconductor
Kind.
Specific embodiment 10: one kind described in specific embodiment six prepares metal rhodium by chemical deposition or rhodium closes
The method of gold, in step (5), the activation processing of metallic matrix is that ion activation or rush of current method activate, semiconductor and non-gold
The activation processing for belonging to matrix is that colloid method activates or ion method activates, and formed by catalytic active particles includes palladium, nickel, rhodium, cobalt, gold, copper.Institute
The formed by catalytic active particles stated, refers to after activation process step, in matrix, including metal, semiconductor and it is nonmetallic it is upper go out
The existing metallic particles to subsequent chemistry deposition reaction with catalytic activity.Such as the example for the palladium being subsequently noted, when matrix is
When metallic copper and Sodium Hypophosphite are reducing agent, the metallic copper as matrix does not have catalytic activity, and chemical deposition reaction can not
Carried out directly on copper, but on metallic copper by replace reaction obtain palladium particle after, palladium be the particle with catalytic activity, put
Chemical deposition can be realized by entering in the solution that Sodium Hypophosphite is reducing agent；For another example when matrix is semiconductor or nonmetallic
When, it is clear that such matrix does not have any catalytic activity, after being activated by colloid palladium, semiconductor or it is nonmetallic on there is metal
Palladium particle, palladium have catalytic activity, so that it may carry out chemical deposition reaction.Certainly, if using metallic nickel as matrix, with hypophosphorous acid
When sodium is reducing agent, nickel has catalytic activity, and such nickel is exactly the matrix with catalytic activity, can be without being activated
Chemical deposition reaction is carried out on nickel.So the premise of formed by catalytic active particles is that matrix does not have catalytic activity, it is after activation processing
Just occur, property has larger difference relative to matrix, either metal, semiconductor or nonmetallic property.With palladium
Particle is made for formed by catalytic active particles: when being activated to the metallic matrix of not catalytic activity, by metallic matrix be put into containing with urge
Change active particle (Pd0) corresponding metal ion (Pd2+) solution in, by displacement react or give short-time current impact,
So that occurring a certain amount of formed by catalytic active particles (Pd on metal base surface0), realize the activation of metallic matrix；It is nonmetallic or half
Conductor matrix activate when, by matrix be put into containing with formed by catalytic active particles (Pd0) (colloid palladium is molten for corresponding colloidal state solution
Liquid) or ionic condition solution (ionic palladium solution) in, pass through the chemical bond of the suction-operated of colloid or ion and matrix surface make
With obtaining the particle (Pd with catalytic activity in matrix surface0).
Embodiment 1:
Rhodium sulfate-EDTA complex object that rhodium content is 1 g/L is prepared by method described in patent CN105906668B
Solution, and pH to 10.0 is adjusted with ammonium hydroxide and sulfuric acid.Red copper matrix is electrolysed after alkali cleaning oil removing and phosphoric acid cleaning, connection power supply is negative
Pole is simultaneously put into the complex solution that temperature is 50 DEG C, using DSA anode connection positive pole as anode, with DC current 2
A/dm2Lower 5 min of electro-deposition, red copper surface obtain the glossiness rhodium layer of white, and corresponding energy spectrum diagram is shown in Fig. 1.The present embodiment pair
The B solution answered is that 0 namely electrodeposition process prepare the technical process of monometallic rhodium, in addition, being carried out clearly with phosphoric acid to red copper matrix
It washes, can both play weak erosion, can also be achieved the weak polishing to red copper matrix.
Embodiment 2:
Radium chloride-EDTA complex object that rhodium content is 1 g/L is prepared by method described in patent CN105906668B
Solution, and pH to 12.0 is adjusted with ammonium hydroxide and hydrochloric acid.Red copper matrix is electrolysed after alkali cleaning oil removing and phosphoric acid cleaning, in chemical nickel plating
One layer of nickel of preplating in liquid connects power cathode and is put into the complex solution for the rhodium that temperature is 40 DEG C, later with DSA anode company
Positive pole is connect as anode, using pulse current, (average current density is 1 A/dm2, duty ratio 33%, 3 ms of period) and plating
5 min, obtain rhodium layer on chemical Ni-plating layer, and energy spectrum diagram is shown in Fig. 2.
Embodiment 3:
(1) radium chloride-EDTA complex that rhodium content is 2 g/L is prepared by method described in patent CN105906668B
Object solution；
(2) mixed solution of the hydrazine containing 2 g/L, 20 mg/L thiocarbamides, 1 g/L PEG-1000 are prepared；
(3) matched solution in (1) and (2) is mixed by the volume ratio of 1:1, is 9.0 with ammonium hydroxide and hydrochloric acid adjustment pH；
(4) red copper matrix is activated in ionic palladium solution after alkali cleaning oil removing and phosphoric acid cleaning, is put into chemical nickel plating later
Chemical nickel plating is carried out in liquid, is taken out washing after 20 min of chemical nickel plating, and be put into step (3) acquired solution, is changed at 80 DEG C
10 min of deposition are learned, the energy spectrum diagram of gained rhodium layer is shown in Fig. 3.The present embodiment corresponds to the work that chemical deposition prepares monometallic rhodium
A and C solution are only mixed in a certain ratio by skill, B solution 0.
Embodiment 4:
(1) rhodium sulfate-ethylenediamine tetra-acetic acid+lemon that rhodium content is 2 g/L is prepared by method described in patent CN105906668B
Lemon acid complex solution；
(2) nickel sulfate-citric acid complex solution that nickel ion content is 2 mol/L is prepared；
(3) it prepares and contains 5 g/L dimethylamino borines, 5 g/L sodium hypophosphites, 20 mg/L thiocarbamides, 20 mg/L dodecyl sulphurs
The mixed solution of sour sodium；
(4) (1), (2), (3) acquired solution are mixed by the volume ratio of 5:1:4, adjusts pH to 5.5 with ammonium hydroxide and sulfuric acid.
(5) red copper matrix is put into the solution after alkali cleaning oil removing and phosphoric acid cleaning, and red copper matrix is accessed DC power supply
Cathode, using DSA anode as anode, with 1 A/dm25 s of rush of current activated, remove external power supply and anode later,
It continues through chemical deposition and deposits 10 min, bath temperature is 60 DEG C, and the energy spectrum diagram of gained nickel rhodium coating is shown in Fig. 4.This
Embodiment corresponds to chemical deposition and prepares rhodium alloy technique, and B solution is no longer 0, and red copper matrix does not have catalytic activity, therefore passes through
Rush of current method obtains the particle with catalytic activity in red copper, and catalysis can occur instead on catalysed particulate after removal power supply
It answers, to realize chemical deposition nickel rhodium.
Claims (10)
1. a kind of method for preparing metal rhodium or rhodium alloy by electrodeposition process, it is characterised in that: the method specific steps
It is as follows:
(1) complex solution for preparing rhodium ion, is denoted as solution A；
(2) complex solution for preparing the dissimilar metal ion that dissimilar metal ion concentration is 2 mol/L, is denoted as B solution；
(3) solution A is mixed with B solution by the volume ratio of 1:0 ~ 10, is adjusted pH value to 5.5 ~ 12 with ammonium hydroxide and acid solution；
(4) matrix Jing Guo pre-treatment is placed in the solution of step (3) preparation, connects power cathode as cathode, separately takes one
Insoluble anode connects positive pole as anode, adjusts electro-deposition process parameter, obtains metal rhodium after 2 ~ 20 min of electro-deposition
Or rhodium alloy；The electro-deposition process parameter includes current waveform and current density, temperature, mixing speed, current waveform packet
Square wave, half-sinusoid, sawtooth wave are included, current density range is 0.5 ~ 3 A/dm2, temperature be 20 ~ 80 DEG C, mixing speed be 0 ~
1000 revs/min.
2. a kind of method for preparing metal rhodium or rhodium alloy by electrodeposition process according to claim 1, it is characterised in that:
The electrodeposition process includes DC electrodeposition and pulse electrodeposition.
3. a kind of method for preparing metal rhodium or rhodium alloy by electrodeposition process according to claim 1, it is characterised in that:
In step (1), 0.1 ~ 10 g/L of concentration of rhodium ion in the complex solution of the rhodium ion；The rhodium ion is by sulfuric acid
One or more of rhodium, phosphoric acid rhodium, radium chloride, iodate rhodium, rhodium nitrate, chlorine rhodate provide.
4. a kind of method for preparing metal rhodium or rhodium alloy by electrodeposition process according to claim 1, it is characterised in that:
In step (2), the dissimilar metal ion is one or more of copper, nickel, zinc, cobalt, iron, chromium, iridium, ruthenium, palladium, gold, silver.
5. a kind of method for preparing metal rhodium or rhodium alloy by electrodeposition process according to claim 1, it is characterised in that:
In step (3), the acid solution is one of sulfuric acid solution, hydrochloric acid solution or phosphoric acid solution；The matrix is metal
Or electrically conductive, non-metallic material.
6. a kind of method for preparing metal rhodium or rhodium alloy by chemical deposition, it is characterised in that: the method specifically walks
It is rapid as follows:
(1) complex solution for preparing rhodium ion, is denoted as solution A；
(2) complex solution for preparing the dissimilar metal ion that dissimilar metal ion concentration is 2 mol/L, is denoted as B solution；
(3) aqueous solution for containing 0.2 ~ 20 g/L reducing agent and 0.1 ~ 200 mg/L additive is prepared, C solution is denoted as；
(4) tri- kinds of solution of A, B, C are mixed by the volume ratio of 1:0 ~ 10:1 ~ 10, is adjusted pH value to 5.5 with ammonium hydroxide and acid solution
~12；
(5) metal, semiconductor or the nonmetal basal body after the metallic matrix with catalytic activity or activation processing are placed in step
(4) in the solution prepared, adjusting process parameter, after 10 ~ 60 min of chemical deposition, i.e., matrix surface obtain corresponding rhodium layer or
Rhodium alloy layer；The technological parameter refers to temperature and mixing speed, and temperature range is 50 ~ 80 DEG C, mixing speed is 0 ~ 500 turn/
Minute.
7. a kind of method for preparing metal rhodium or rhodium alloy by chemical deposition according to claim 6, feature exist
In: in step (1), 0.1 ~ 10 g/L of concentration of rhodium ion in the complex solution of the rhodium ion；The rhodium ion is by sulphur
One or more of sour rhodium, phosphoric acid rhodium, radium chloride, iodate rhodium, rhodium nitrate, chlorine rhodate provide.
8. a kind of method for preparing metal rhodium or rhodium alloy by chemical deposition according to claim 6, feature exist
In: in step (2), the dissimilar metal ion is one or more of nickel, cobalt, palladium, gold, copper, ruthenium, silver.
9. a kind of method for preparing metal rhodium or rhodium alloy by chemical deposition according to claim 6, feature exist
In: in step (3), the reducing agent is one of amino borane, hydrazine, sodium borohydride, sodium hypophosphite, formaldehyde, glyoxalic acid
And a variety of mixture；The additive is thiocarbamide, lead ion, UPS, Potassiumiodate, potassium iodide, saccharin, the potassium ferricyanide, ferrous iron
The mixture of one or more of potassium cyanide, potassium rhodanide, dodecyl sodium sulfate and PEG；The acid solution is sulfuric acid
One of solution, hydrochloric acid solution or phosphoric acid solution；The matrix is one of metal, nonmetallic or semiconductor.
10. a kind of method for preparing metal rhodium or rhodium alloy by chemical deposition according to claim 6, feature exist
In: in step (5), the activation method of metallic matrix is that ion activation or rush of current method activate, nonmetallic and semiconductor material
Activation be colloid method activate or ion method activation, formed by catalytic active particles includes palladium, nickel, rhodium, cobalt, gold, copper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811154290.XA CN109097800A (en) | 2018-09-30 | 2018-09-30 | A method of metal rhodium or rhodium alloy are prepared by electro-deposition or chemical deposition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811154290.XA CN109097800A (en) | 2018-09-30 | 2018-09-30 | A method of metal rhodium or rhodium alloy are prepared by electro-deposition or chemical deposition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109097800A true CN109097800A (en) | 2018-12-28 |
Family
ID=64867794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811154290.XA Pending CN109097800A (en) | 2018-09-30 | 2018-09-30 | A method of metal rhodium or rhodium alloy are prepared by electro-deposition or chemical deposition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109097800A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109811331A (en) * | 2019-02-27 | 2019-05-28 | 西京学院 | A kind of silicon face coating and its preparation process and purposes |
| CN111850631A (en) * | 2020-07-30 | 2020-10-30 | 金川集团股份有限公司 | High-gloss decorative rhodium-plated layer electroplating solution |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101663753A (en) * | 2007-04-20 | 2010-03-03 | 国际商业机器公司 | Fabricating a contact rhodium structure by electroplating and electroplating composition |
| CN102171387A (en) * | 2008-10-04 | 2011-08-31 | 尤米科尔电镀技术有限公司 | Process for the deposition of platinum-rhodium layers having improved whiteness |
| CN104854120A (en) * | 2012-12-12 | 2015-08-19 | 优美科股份公司及两合公司 | Method for producing aqueous preparations of complexes of platinum group metals |
| CN105906668A (en) * | 2016-05-03 | 2016-08-31 | 哈尔滨工业大学 | Complexing agent for trivalent rhodium ions in alkaline solution and direct liquid phase preparation method for complex of trivalent rhodium ions |
-
2018
- 2018-09-30 CN CN201811154290.XA patent/CN109097800A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101663753A (en) * | 2007-04-20 | 2010-03-03 | 国际商业机器公司 | Fabricating a contact rhodium structure by electroplating and electroplating composition |
| CN102171387A (en) * | 2008-10-04 | 2011-08-31 | 尤米科尔电镀技术有限公司 | Process for the deposition of platinum-rhodium layers having improved whiteness |
| CN104854120A (en) * | 2012-12-12 | 2015-08-19 | 优美科股份公司及两合公司 | Method for producing aqueous preparations of complexes of platinum group metals |
| CN105906668A (en) * | 2016-05-03 | 2016-08-31 | 哈尔滨工业大学 | Complexing agent for trivalent rhodium ions in alkaline solution and direct liquid phase preparation method for complex of trivalent rhodium ions |
Non-Patent Citations (6)
| Title |
|---|
| DUNJA CUKMAN等: "Electrochemical behaviour of an electrodeposited rhodium electrode in alkaline solution", 《J. ELECTROANAL. CHEM》 * |
| 张招贤等: "《钛电极反应工程学》", 30 April 2009, 冶金工业出版社 * |
| 戴春爱等: "《工科化学》", 31 August 2018, 北京交通大学出版社 * |
| 牛飞等: "贵金属铑电镀液的研究进展", 《黄金》 * |
| 郑振等: "《表面精饰用化学品》", 30 January 2002, 中国物资出版社 * |
| 韩寿山: "《电镀技术在电子工业中的应用》", 30 September 1980, 国防工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109811331A (en) * | 2019-02-27 | 2019-05-28 | 西京学院 | A kind of silicon face coating and its preparation process and purposes |
| CN111850631A (en) * | 2020-07-30 | 2020-10-30 | 金川集团股份有限公司 | High-gloss decorative rhodium-plated layer electroplating solution |
| CN111850631B (en) * | 2020-07-30 | 2021-10-08 | 金川集团股份有限公司 | High-gloss decorative rhodium-plated layer electroplating solution |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102037162B (en) | Pd and Pd-Ni electrolyte baths | |
| CN102747345B (en) | Method for chemically plating nickel on surface of copper circuit of PCB (printed circuit board) by dipping and activating nickel | |
| JP2011520036A5 (en) | ||
| JP6370380B2 (en) | Electrolyte for electrodeposition of silver-palladium alloy and deposition method thereof | |
| CN106460179A (en) | Nickel colloid catalyst solution for electroless nickel or nickel alloy plating, and electroless nickel or nickel alloy plating method | |
| CN103668358B (en) | A kind of method of pulse non-cyanide silver electroplating | |
| CN101760768A (en) | Electroplating solution for cyanide-free silver plating and cyanide-free silver plating method | |
| CN101260549B (en) | Non-preplating type non-cyanide silver-plating electroplate liquid | |
| CN109097800A (en) | A method of metal rhodium or rhodium alloy are prepared by electro-deposition or chemical deposition | |
| JP4790191B2 (en) | Electrolytic bath for electrochemical deposition of palladium or its alloys | |
| CN109957822A (en) | Copper alloy electroplating technology | |
| CN109852952A (en) | A kind of hydrazine hydrate chemical nickel-plating plating solution and preparation method thereof and nickel plating process | |
| KR20120081107A (en) | Process for applying a metal coating to a non-conductive substrate | |
| CN100424232C (en) | Nickel electric plating liquid | |
| JP4740508B2 (en) | Palladium complex salts and their use to adjust the palladium concentration of electrolytic baths for depositing palladium or one of its alloys | |
| EP0059452B1 (en) | Palladium and palladium alloys electroplating procedure | |
| CN114921704A (en) | Cobalt-nickel-molybdenum-based composite material, preparation method thereof, hydrogen evolution electrode based on cobalt-nickel-molybdenum-based composite material and household appliance | |
| KR102295180B1 (en) | Ag-Nano Alloy Plating Solution Compositions for Improving of Conductivity and Durability and Plating Methods Using Thereof | |
| JP5838431B1 (en) | Production method and zinc dissolution method | |
| CN106232869A (en) | Ferroboron coating and preparation method thereof | |
| JP5025815B1 (en) | Hard gold plating solution | |
| CN110453256B (en) | Polyhedral cobalt-iridium nanoparticle hydrogen evolution electrocatalyst, plating solution and preparation method thereof | |
| TW200303939A (en) | Nickel electroplating solution | |
| EP3686319A1 (en) | Indium electroplating compositions and methods for electroplating indium on nickel | |
| JP4447100B2 (en) | Alkaline zinc and zinc alloy plating bath |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181228 |
|
| RJ01 | Rejection of invention patent application after publication |