CN108130570A - A kind of compound trivalent plating chromium process - Google Patents

A kind of compound trivalent plating chromium process Download PDF

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Publication number
CN108130570A
CN108130570A CN201711344091.0A CN201711344091A CN108130570A CN 108130570 A CN108130570 A CN 108130570A CN 201711344091 A CN201711344091 A CN 201711344091A CN 108130570 A CN108130570 A CN 108130570A
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plating
electroplate liquid
electroplating
coating
metal
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黄进峰
杨兵
解国良
连勇
张津
陈新
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Beijing University of Technology
University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • 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
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers

Abstract

The present invention provides a kind of metal surface composite chrome plating technique and plating solution formula.The method divides slot electroplating technology using segmentation：It plates the layers of chrome of one layer of 20 30um in metal surface according to a conventional method first, secondly, the metal material of chrome layer is placed in another electroplating bath and carries out second time electroplating, nano-silicon nitride is added in second time electroplating liquid.Due to the rigidity of nano-silicon nitride itself, coating can be uniformly dispersed in electroplating process, so as to improve the hardness of coating and wearability.On the one hand the nano-silicon nitride uniformly dispersed in coating can be covered in chromium metal grain surface to prevent the infiltration of corrosive liquid by the hole and winding for filling coating, on the other hand by forming miniature galvanic cell with chromium metal grain, promote the Dunhua of chromium, which thereby enhance corrosion resisting property.Metal material forms compound electroplated layer by being electroplated twice, and the electroplated layer is uniform in metal surface publication, and hardness reaches HV900 1200, superior performance, is with a wide range of applications and economic value.

Description

A kind of compound trivalent plating chromium process
Technical field
The invention belongs to field of electroplating, and in particular to a kind of raising chromium plating layer thickness, case hardness, corrosion resistance, wearability Electroplating technology.
Background technology
At present, chromium plating has become one of most widely used plating in electroplating industry.For a long time, chromium plating using Hexavalent chromium plating technique wherein the chromic acid toxicity as hexavalent chromium supplier is very big, can cause skin to occur burning and burst Ulcer makes operator suffer from the occupational diseases such as skin macula, perforation of nasal septum, and has strong carcinogenesis to human body.It can lead simultaneously Soil stomata obstruction is caused, destroys soil texture.These phenomenons have caused the extensive concern of people, with constantly enhancing for people Environmental consciousness, the research of trivalent electrodeposited chromium and improve coating surface hardness, corrosion resistance, wearability electroplating technology increasingly by To the favor of people.
But trivalent chrome plating has the following problems at present：
(1) coating buildup thickness is difficult：The thickness of trivalent chrome plating generally only has several microns, main cause plating solution pH at present Value and temperature are increased with the increase of electroplating time, are aggravated so as to cause evolving hydrogen reaction, and final cathode current is entirely used for analysing Hydrogen and make chromium electro-deposition stop.
Trivalent chromic ion is very easy to be oxidized into Cr VI and influences trivalent chromium electricity also in anode in electroplating process Original causes coating that cannot continue to thicken.
(2) plating solution composition is complicated.Not only type is various for bath system at present, but also all contains a large amount of additive.In addition, Other metal impurities that anode is brought into etc. all make the management service of plating solution extremely difficult, and the popularization for also limiting trivalent chromium plating should With.
(3) conventional trivalent electrodeposited chromium technology is only applied at present due to the system of its case hardness, thickness and its wearability On ornament, there are no realize commercial Application.
It is difficult to improve case hardness simultaneously using conventional trivalent electrodeposited chromium technology, surface abrasion resistance and corrosion resistance.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of compound trivalent plating chromium process, and the method uses segmentation, Slot is divided to be electroplated to form compound trivalent chrome plating.Boric acid is added in the present invention in electroplate liquid to stablize the pH value of plating solution, with And a thermostat is placed below electroplating bath to stablize the temperature of plating solution, reduce evolving hydrogen reaction so as to be conducive to Coating thickens.
Since coated titanium anode has easy to use, more corrosion-resistant, the advantages of service life is longer, applied on Titanium base Coated anode of the yttrium oxide as electrode catalyst layer can avoid the formation of Cr VI, and can prevent and eliminate to be formed on anode Body refuse, keep the stabilization of plating solution for a long time.
Also contain nano-silicon nitride in the plating solution of the present invention, it, can in electroplating process due to the rigidity of nano-silicon nitride itself To be uniformly dispersed in coating, so as to improve the hardness of coating and wearability；
On the one hand the nano-silicon nitride uniformly dispersed in coating can be covered in chromium by the hole and winding for filling coating Metal grain surface, on the other hand by forming miniature galvanic cell with chromium metal grain, promotes chromium to prevent the infiltration of corrosive liquid Dunhua, which thereby enhance corrosion resisting property.Thickness of coating can be made to reach 50-70um using the plating chromium process.Coating surface Hardness reaches 900HV -1200HV, and corrosion resistance, wearability reach the level of sexavalence coating.
A kind of compound trivalent plating chromium process, it is characterised in that using graphite electrode as anode, to need the Metal Substrate being electroplated Body is cathode, and plating step is as follows：
Step 1：Oil removing, polishing, washing, pickling are carried out to cathode base using the art conventional technique method Processing；
Step 2：Electroplate liquid one is poured into electrolytic cell one, the temperature of electrolytic cell one is raised to 30 DEG C, to electroplating bath into Row, which is powered, to be started to be electroplated, and the chrome plating that thickness is 20-30um is plated in metal surface；
Step 3：Second time electroplating pours into electroplate liquid two in electrolytic cell two, and the temperature of electroplate liquid two is raised to 30 DEG C, and And a constant temperature blender with magnetic force is put below electroplating bath two；It is clear that the metal of chromium plating in step 2 is carried out to surface again Wash, be placed into electrolytic cell two and carry out second time electroplating, and open constant temperature blender with magnetic force, formed again on the surface of coating containing Nano particle Si3N4Chrome layer；
The ingredient of wherein electroplate liquid one is：Cr3+04-0.8mol·dm-3, HCOOH 0.4-1.0moldm-3, CH3OH 0.2-0.5mol·dm-3, NH4Br 0.2-0.3mol·dm-3, Na2SO4 1.5-2.0mol·dm-3, H3BO3 0.8- 1.2mol·dm-3, C12H25SO4Na 0.005mol·dm-3；
The ingredient of electroplate liquid two is：Cr3+04-0.8mol·dm-3, HCOOH 0.4-1.0moldm-3, CH3OH 0.2- 0.5mol·dm-3, NH4Br 0.2-0.3mol·dm-3, Na2SO41.5-2.0mol·dm-3, H3BO30.8-1.2mol·dm-3, C12H25SO4Na 0.005mol·dm-3、Si3N42-8g·L-1。
Further, the Si that granular size is 20-50nm in plating solution two3N4Content is 4-8g/L.
Further, the preparation method of the electroplate liquid two is：The reagent of each raw material components is soluble in water, then will metering The nano-silicon nitride is dissolved in wherein, is disperseed after mixing with ultrasonic wave.The ultrasonic wave dispersion power is 600- 1000w, the time of ultrasonic wave dispersion is 5-6min.
A kind of trivalent chromium plating technology of the present invention, using graphite electrode as anode, graphite material convenient material drawing is cheap, Electroplating efficiency and electroplating effect are all very good, the material of chromium plating to be needed to be removed before plating to cathode base as cathode The processing such as oil, polishing, washing, pickling.Ensure that the coating obtained during plating has sufficiently large adhesive force.Water-insoluble is received Rice solia particle Si3N4 is added in electroplating solution, it is made to be co-deposited on base material with base metal in electroplating process, these Particle, which is dispersed in coating, can effectively refine metal grain to improve the mechanical property of metal and corrosion resistance.
Trivalent chromium plating reaction principle of the present invention is as follows：In cloudy Cr3+Electroreduction be divided into two points of progress, wherein the first step is Cr3+Single electron will definitely back reaction, have catalysis reaction characteristic, that is, the Cr generated2+It can be by the H in solution+It is reoxidized For Cr3+(reaction 1-1)；Second step is Cr2+It is reduced to the irreversible reaction (reaction 2-7) of metal Cr.
Cr3++e-→Cr2+ (1-1)
Cr2++2e-→2Cr (1-2)
It is mainly water electric discharge generation oxygen and chlorion generation chlorine in anode.Meanwhile in electrolyte, formic acid, with Chromium ion is complexed to form more stable complex ion, and trivalent chromic ion is made to be more easy to discharge, promote the deposition of crome metal.Formates The HCOO provided-Ligand can be with Cr3+Complex is formed, so as to adjust the discharge potential of complex ion.Meanwhile formic acid is in plating solution In can also play cushioning effect.Boric acid makes bath pH value in electroplating process be maintained in certain range.Sulfate improves plating solution Electric conductivity reduces tank voltage.
Nano-silicon nitride formation includes two step adsorption processes in composite deposite in the present invention:The first step is weak reversible physical Absorption, i.e. surface carry ion and the particle of solvent molecule is adsorbed on cathode surface；Second step is strong irreversible electrification Absorption is learned, i.e., the ion adsorbed with a part on surface is reduced, and particle occurs strong absorption with cathode and enters coating.
The composite galvanized coating hardness that chromium process formation is electroplated by compound trivalent provided by the invention reaches HV900-1200, Due to containing nano particle Si in outmost chrome layer3N4,
Therefore, wearability and corrosion resistance are twice of conventional coating performance.Physical property, coating structure optimization, Mechanical performance is also optimized.
The energizing step of chrome-plating method step 2 and step 3 of the present invention is carried out by the art common technology method, just To electric current depending on the surface area of workpiece, generally using 25-33A/dm2.The time of forward current is according to the thickness of coating Depending on.
Chrome-plating method of the present invention is suitable for the common metal material of mechanical industry, steel etc..
Description of the drawings
Fig. 1 is apparatus of the present invention structure chart,
1. getter device, 3. the Titanium base anode for being 2. coated with yttrium oxide, temperature constant magnetic stirring, 4. temperature constant magnetic stirring Device, 5. plating piece, 6. D.C. regulated power supply
Specific embodiment
Embodiment one：
Concrete operations：
By following recipe configuration electroplate liquid one and electroplate liquid two：
Electroplate liquid one：CrCl3.6H2O 106g/L, CHooH 9.2g/L；
Electroplate liquid two：CrCl3.6H2O 110g/L, CHooH 9.8g/L, Si3N4 6g·L-1。
Metal material is electroplated by following operative step：
Step 1：Oil removing, polishing, washing, pickling are carried out to metal surface using the art conventional technique method Processing, makes metal surface activation.
Step 2：Electroplate liquid one is poured into electrolytic cell one, the temperature of electrolytic cell one is raised to 30 DEG C, it will be in step 1 The metal of surface active is put into electrolytic cell one.Electroplating bath be powered and starts to be electroplated.5min is electroplated, thickness is plated in metal surface Spend the chrome plating for 20-30um.
Step 3：Second time electroplating pours into electroplate liquid two in electrolytic cell two, and the temperature of electroplate liquid two is raised to 30 DEG C, and And a constant temperature blender with magnetic force is put below electroplating bath two.It is clear that the metal of chromium plating in step 2 is carried out to surface again It washes, is placed into electrolytic cell two and carries out second time electroplating, and open constant temperature blender with magnetic force, rotating speed is maintained at 200r/min.Plating 10min is formed again on the surface of coating containing nano particle Si3N4Chrome layer.·
Embodiment two：
Concrete operations：
By following recipe configuration electroplate liquid one and electroplate liquid two：
Electroplate liquid one：CrCl3.6H2O 106g/L, CHooH 9.2g/L；
Electroplate liquid two：CrCl3.6H2O 110g/L, CHooH 9.8g/L, Si3N4 8g·L-1。
Metal material is electroplated by following operative step：
Step 1：No. 45 steel discs (3cm × 4cm, thickness 2mm) are carried out using the art conventional technique method Oil removing, polishing, washing, pickling processes, make metal surface activation.
Step 2：Electroplate liquid one is poured into electrolytic cell one, the temperature of electrolytic cell one is raised to 30 DEG C, it will be in step 1 The metal of surface active is put into electrolytic cell one.Electroplating bath be powered and starts to be electroplated.5min is electroplated, thickness is plated in metal surface Spend the chrome plating for 20-30um.
Step 3：Second time electroplating pours into electroplate liquid two in electrolytic cell two, and the temperature of electroplate liquid two is raised to 30 DEG C, and And a constant temperature blender with magnetic force is put below electroplating bath two.It is clear that the metal of chromium plating in step 2 is carried out to surface again It washes, is placed into electrolytic cell two and carries out second time electroplating, and open constant temperature blender with magnetic force, rotating speed is maintained at 300r/min.Plating 10min is formed again on the surface of coating containing nano particle Si3N4Chrome layer.
Embodiment three：
Concrete operations：
By following recipe configuration electroplate liquid one and electroplate liquid two：
Electroplate liquid one：CrCl3.6H2O 101g/L, CHooH 9.1g/L；
Electroplate liquid two：CrCl3.6H2O 110g/L, CHooH 9.8g/L, Si3N4 6g·L-1。
Purity is used in the present embodiment, and for 99.9% copper plate test specimen, specification is 3cm × 4cm, thickness 2mm, right Its metal material is electroplated：
Step 1：Oil removing, polishing, washing, pickling are carried out to metal surface using the art conventional technique method Processing, makes metal surface activation.
Step 2：Electroplate liquid one is poured into electrolytic cell one, the temperature of electrolytic cell one is raised to 30 DEG C, it will be in step 1 The metal of surface active is put into electrolytic cell one.Electroplating bath be powered and starts to be electroplated.5min is electroplated, is plated in red copper plate surface Thickness is the chrome plating of 20-30um.
Step 3：Second time electroplating pours into electroplate liquid two in electrolytic cell two, and the temperature of electroplate liquid two is raised to 30 DEG C, and And a constant temperature blender with magnetic force is put below electroplating bath two.It is clear that the metal of chromium plating in step 2 is carried out to surface again It washes, is placed into electrolytic cell two and carries out second time electroplating, and open constant temperature blender with magnetic force, rotating speed is maintained at 400r/min.Plating 10min is formed again on the surface of coating containing nano particle Si3N4Chrome layer.·
Example IV：
Concrete operations：
By following recipe configuration electroplate liquid one and electroplate liquid two：
Electroplate liquid one：CrCl3.6H2O 110g/L, CHooH 9.6g/L；
Electroplate liquid two：CrCl3.6H2O 110g/L, CHooH 9.6g/L, Si3N4 8g·L-1。
304 stainless steel metal materials are electroplated by following operative step：
Step 1：Using the art conventional technique method to 304 stainless steels (3cm × 4cm, thickness 2mm) gold Metal surface carries out oil removing, polishing, washing, pickling processes, makes metal surface activation.
Step 2：Electroplate liquid one is poured into electrolytic cell one, the temperature of electrolytic cell one is raised to 30 DEG C, it will be in step 1 The metal of surface active is put into electrolytic cell one.Electroplating bath be powered and starts to be electroplated.5min is electroplated, thickness is plated in metal surface Spend the chrome plating for 20-30um.
Step 3：Second time electroplating pours into electroplate liquid two in electrolytic cell two, and the temperature of electroplate liquid two is raised to 30 DEG C, and And a constant temperature blender with magnetic force is put below electroplating bath two.It is clear that the metal of chromium plating in step 2 is carried out to surface again It washes, is placed into electrolytic cell two and carries out second time electroplating, and open constant temperature blender with magnetic force, rotating speed is maintained at 600r/min.Plating 10min is formed again on the surface of coating containing nano particle Si3N4Chrome layer.·
Comparative example：
In addition to not other than silicon nitride comprising, other conditions are identical with embodiment two in plating solution.
Interpretation of result：
Coating corrosion resistance is tested：
Vickers (load 100kg) is used, conical surface angle is 136 ° of diamond four directions pyramid pressure, is paid attention to Ensure that pressure head pressure people's depth should be less than 1/10th of surface thickness, 15s is kept to measure coating hardness.Bottom left is taken during test The identation hardness value of right and intermediate five points, then be averaged.
Coating corrosion resistance is tested：
Using complete immersion zero-G test method, composite deposite test agent is invaded respectively 20% NaOH solution and 3.5% NaCl solution in, the erosion test duration is respectively 240h and 340h, while it is 30 DEG C to keep corrosive medium temperature, so The weightlessness after it corrodes is measured afterwards, acquires corrosion rate.Sample is rinsed by deionized water before and after corrosion, and ethyl alcohol surpasses Sound is cleaned, is dried in vacuo, four steps of weighing.Corrosion rate is calculated according to the following formula：Corrosion rate=(quality before corrosion- Quality after corrosion)/(etching time × corrosion surface product).
Wearability test：
Friction-wear test carries out on SRV type abrasion testers, is the quenching of the chrome-bearing steel of diameter 10nm to mill sample Steel ball, Rockwell hardness 58-60, steel ball surface roughness are less than 0.4um；Experiment atmosphere at room temperature environment, it is unlubricated, without abrasive material Under the conditions of carry out, hardened steel ball reciprocatingly slides in chrome-plated surface, stroke 2mm, frequency 30Hz, load 60N.
Thickness of coating is tested：
Using weight method.Specifically, by plating piece by polishing, quality is weighed after the processes such as oil removing, washing, drying, then It is electroplated again, weighs quality after being electroplated again, according to the following formula calculated thickness：The average thickness of coating=(plating piece is electroplated Quality before quality afterwards-plating piece plating)/(density of surface area × coated metal of coating institute covering part), surface area Unit is cm2, mass unit g, the density unit for plating metal is g/ml.
Test result is as follows for embodiment one, two and comparative example coating performance：
As can be seen from the above table, embodiment one, two thickness of coating and Vickers hardness are apparently higher than comparative example, 30min Wear extent and corrosion rate are substantially better than comparative example.This illustrates that nano particle silicon nitride significantly improves the hardness of coating, wear-resisting Property and corrosion resistance.

Claims (3)

1. a kind of compound trivalent plating chromium process, it is characterised in that using graphite electrode as anode, to need the metallic matrix being electroplated For cathode, plating step is as follows：
Step 1：Oil removing, polishing, washing, pickling processes are carried out to cathode base using the art conventional technique method；
Step 2：Electroplate liquid one is poured into electrolytic cell one, the temperature of electrolytic cell one is raised to 30 DEG C, is powered to electroplating bath Start to be electroplated, the chrome plating that thickness is 20-30um is plated in metal surface；
Step 3：Second time electroplating pours into electroplate liquid two in electrolytic cell two, and the temperature of electroplate liquid two is raised to 30 DEG C, and A constant temperature blender with magnetic force is put below electroplating bath two；The metal of chromium plating in step 2 is subjected to surface clean again, is put Second time electroplating is carried out, and open constant temperature blender with magnetic force in merging electrolytic cell two, formed again containing nanometer on the surface of coating Particle Si3N4Chrome layer；
The ingredient of wherein electroplate liquid one is：Cr3+04-0.8mol·dm-3, HCOOH 0.4-1.0moldm-3, CH3OH 0.2- 0.5mol·dm-3, NH4Br 0.2-0.3mol·dm-3, Na2SO4 1.5-2.0mol·dm-3, H3BO3 0.8-1.2mol·dm-3, C12H25SO4Na 0.005mol·dm-3；
The ingredient of electroplate liquid two is：Cr3+04-0.8mol·dm-3, HCOOH 0.4-1.0moldm-3, CH3OH 0.2- 0.5mol·dm-3, NH4Br 0.2-0.3mol·dm-3, Na2SO4 1.5-2.0mol·dm-3, H3BO3 0.8-1.2mol·dm-3, C12H25SO4Na 0.005mol·dm-3、Si3N4 2-8g·L-1。
2. a kind of compound trivalent plating chromium process according to claim 1, it is characterised in that granular size is in plating solution two The Si of 20-50nm3N4Content is 4-8g/L.
A kind of 3. compound trivalent plating chromium process according to claim 1, it is characterised in that the preparation of the electroplate liquid two Method is：The reagent of each raw material components is soluble in water, then be dissolved in the nano-silicon nitride is measured wherein, after mixing Disperseed with ultrasonic wave.The ultrasonic wave dispersion power is 600-1000w, and the time of ultrasonic wave dispersion is 5-6min.
CN201711344091.0A 2017-12-15 2017-12-15 A kind of compound trivalent plating chromium process Pending CN108130570A (en)

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CN110760789A (en) * 2019-11-04 2020-02-07 丽水市建川五金制造有限公司 Surface fine treatment process for surface treatment door handle
CN111321433A (en) * 2020-02-25 2020-06-23 光山白鲨针布有限公司 Electroplating solution for chromium-based card clothing
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