CN103806041A - Cyanide-free copper-zinc alloy electroplating solution and preparation method thereof - Google Patents
Cyanide-free copper-zinc alloy electroplating solution and preparation method thereof Download PDFInfo
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- CN103806041A CN103806041A CN201410014014.9A CN201410014014A CN103806041A CN 103806041 A CN103806041 A CN 103806041A CN 201410014014 A CN201410014014 A CN 201410014014A CN 103806041 A CN103806041 A CN 103806041A
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Abstract
The invention relates to a cyanide-free copper-zinc alloy electroplating solution and a preparation method thereof. The electroplating solution consists of the following components in percentage by weight: 1-60 percent of complexing agent, 0.3-10 percent of copper salt, 0.2-10 percent of zinc salt and the balance of water, wherein the general formula of the complexing agent is MxHyPnO(3n+1)Rz; M is any one or multiple in alkali metal ions and NH<4+>; R is acyl; the general formula of the copper salt is Cux/2HyPnO(3n+1)Rz; the general formula of the zinc salt is Znx/2HyPnO(3n+1)Rz; x, n and z are positive integers; y is 0 or a positive integer; x+y+z is equal to n+2. The cyanide-free copper-zinc alloy electroplating solution is prepared by mixing the complexing agent, the copper salt, the zinc salt and water, the complexing capacity of the complexing agent is high, the complexing constant of copper ions can be 10<26-27>, and the complexing agent is far superior to a conventional complexing agent in the prior art. The stability of the electroplating solution prepared from the complexing agent is greatly improved, the quality of the electroplating solution is high, when the cyanide-free electroplating solution is used for pre-plating, main salt metal ions in the electroplating solution are not subjected to a replacement reaction with a metal base material, a loose replacement layer structure is not formed, and the quality of the electroplating layer is greatly improved.
Description
Technical field
The present invention relates to a kind of electroplate liquid, relate to specifically one without cyanogen copper zinc alloy electroplate liquid and preparation method thereof, belong to Cu electroplating zinc technical field.
Background technology
Copper zinc alloy coating has flavous outward appearance, but also can carry out in its surface chemical stain, to reach special decorative effect, therefore, be widely used in decorative coating, but because the standard potential of copper, zinc differs larger, therefore can not obtain desirable alloy layer from single salts solution, still there is no so far a kind of electroplate liquid of replacement cyanide electroplating zinc alloy that can be satisfied.
Although the copper zinc coating that adopts the copper zinc alloy electroplate liquid (being cupric cyanide zinc electroplate liquid) that contains prussiate to obtain is careful, bonding force good, and all platings of electroplate liquid, leveling property and stability are also very good.But prussiate is severe poisonous chemicals, it is only 0.005g to people's lethal quantity, and prussiate had both endangered the healthy of operator, simultaneously contaminate environment again, and also waste water is difficult to administer, and its sewage disposal expense is high.Therefore for protection of the environment, reduce public hazards, urgently exploitation is a kind of without cyanogen copper zinc electroplate liquid.
Summary of the invention
The cupric cyanide zinc electroplate liquid that the object of the invention is to solve prior art is containing toxic substance cyanogen, affect operator's health, contaminate environment, and the reluctant deficiency of its waste water, a kind of copper zinc alloy electroplate liquid that does not contain cyanogen is provided, this electroplate liquid does not contain cyanogen, environmental friendliness, manufacture, storage and safe and convenient to use.
Another object of the present invention is to provide a kind of preparation method without cyanogen copper zinc alloy electroplate liquid.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of without cyanogen copper zinc alloy electroplate liquid, it is characterized in that: described electroplate liquid is made up of the component of following weight percent: complexing agent 1～60%, mantoquita 0.01～10%, zinc salt 0.01～10%, surplus is water, the general formula of described complexing agent is M
xh
yp
no
3n+1r
z, wherein M be in alkalimetal ion and NH4+ any one or multiple, R is acyl group, the general formula of mantoquita is Cu
x/2h
yp
no
3n+1r
z, the general formula of zinc salt is Zn
x/2h
yp
no
3n+1r
z, described x, n and z are positive integer, and y is 0 or positive integer, x+y+z=n+2.
Below with several examples to explain the structure of complexing agent in above-mentioned component:
A: work as x=1, when y=1, z=n, the general formula of complexing agent is MHP
no
3n+1r
n, its structural formula as the formula (1):
B: work as x=n, when y=0, z=2, is M when complexing agent
np
no
3n+1r
2, its structural formula as the formula (2):
C: work as x=1, when y=n-1, R=2, the general formula of complexing agent is MH
n-1p
no
3n+1r
2, its structural formula as the formula (1):
Of the present inventionly be mixed into by complexing agent, mantoquita, zinc salt and water without cyanogen copper zinc alloy electroplate liquid, wherein the complex ability of complexing agent is strong, can reach 10 to the complexation constant of cupric ion
26～27be far superior to conventional complexing agent of the prior art, the stability of the electroplate liquid being made by this complexing agent improves greatly, the quality of electroplate liquid is high, this cyanideless electro-plating liquid when the preplating, the main salt metal ion in electroplate liquid not can with metal base generation replacement(metathesis)reaction, can not produce loose displacement layer structure, therefore, the bonding force of electrolytic coating and metal base is strong and coating surface is level and smooth, and the quality of electrolytic coating is greatly improved.
As preferably, described electroplate liquid is made up of the component of following weight percent: complexing agent 20～45%, and mantoquita 0.5～10.0%, zinc salt 0.2～5.0%, surplus is water, the general formula of described complexing agent is M
xh
yp
no
3n+1r, wherein M is Na
+, K
+with in NH4+ any one or multiple, R is acyl group, the general formula of mantoquita is Cu
x/2h
yp
no
3n+1r, the general formula of zinc salt is Zn
x/2h
yp
no
3n+1r, described x and n are positive integer, and y is 0 or positive integer, x+y=n+1.
Below with several examples to explain the composition of the complexing agent in this optimal technical scheme:
D: in the time of y=0, x=n+1, the general formula of complexing agent is M
n+1p
no
3n+1r, its structural formula as the formula (4):
structural formula (4);
E: in the time of y=1, x=n, the general formula of complexing agent is M
nhP
no
3n+1r, its structural formula as the formula (5):
F: in the time of y=n-1, x=2, the general formula of complexing agent is M
2h
n-1p
no
3n+1r, its structural formula as the formula (6):
Without a preparation method for cyanogen copper zinc alloy electroplate liquid, the preparation method of described electroplate liquid is as follows:
(1) preparation of complexing agent: by containing alkali, carbonate or the supercarbonate of M with phosphoric acid, containing the monobasic organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution is at next step polymerase 10 of 100～800 ℃ of conditions .5～10h acquisition complexing agent finished product; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5～10h obtains complexing agent finished product under 100～800 ℃ of conditions;
(2) preparation of mantoquita: the complexing agent that step (1) is made mixes in molar ratio with cupric compound in aqueous phase system, in 25～100 ℃ of reaction 0.5～1h, is also dried and obtains mantoquita through centrifugation after reaction finishes;
(3) preparation of zinc salt: the complexing agent that step (1) is made mixes in molar ratio with divalent zinc compound in aqueous phase system, in 25～100 ℃ of reaction 0.5～1h, is also dried and obtains zinc salt through centrifugation after reaction finishes;
(4) preparation of electroplate liquid: the complexing agent of step (1) is dissolved in suitable quantity of water, then in proportion the zinc salt of the mantoquita of step (2) and step (3) is dissolved in above-mentioned complexing agent aqueous solution, the water that fills into again surplus mixes, then adjust pH to 8.5～9.5, obtain without cyanogen copper zinc alloy electroplate liquid.
Preparation method without cyanogen copper zinc alloy electroplate liquid of the present invention is simple to operate, production cost is low, product cost performance is high, drying mode in step (1) is for spraying is dry or expansion drying, whole preparation technology's environmental friendliness, the charging capacity of step (1) and step (2) is accurate, and feed stock conversion approaches 100%, in reacted waste water, foreign matter content is low, and cost for wastewater treatment is low.
As preferably, when M is Na
+time, the preparation manipulation of complexing agent is as follows in step (1): by sodium hydroxide, sodium carbonate or sodium bicarbonate, with phosphoric acid, containing the monobasic organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution is at next step polymerase 10 of 200～400 ℃ of conditions .5～10h acquisition complexing agent finished product; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5～10h obtains complexing agent finished product under 200～400 ℃ of conditions.
As preferably, when M is K
+time, the preparation manipulation of complexing agent is as follows in step (1): by potassium hydroxide, salt of wormwood or saleratus, with phosphoric acid, containing the monobasic organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution is at next step polymerase 10 of 250～800 ℃ of conditions .5～10h acquisition complexing agent finished product; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5～10h obtains complexing agent finished product under 250～800 ℃ of conditions.
As preferably, in the time that M is NH4+, the preparation manipulation of complexing agent is as follows in step (1): by ammoniacal liquor, volatile salt or bicarbonate of ammonia, with phosphoric acid, containing the monobasic organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution is at next step polymerase 10 of 100～300 ℃ of conditions .5～10h acquisition complexing agent finished product; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5～10h obtains complexing agent finished product under 100～300 ℃ of conditions.
Except the above-mentioned mantoquita of listing, zinc salt, of the present inventionly can also directly be selected from any one or a few in copper sulfate, cupric chloride or ventilation breather without the mantoquita in cyanogen copper zinc alloy electroplate liquid, zinc salt can also directly be selected from any one or a few in zinc sulfate, zinc chloride or zinc subcarbonate, in the time adopting this technical scheme, the described preparation method without cyanogen copper zinc alloy electroplate liquid is as follows:
(1) preparation of complexing agent: by containing alkali, carbonate or the supercarbonate of M with phosphoric acid, containing the monobasic organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution is at next step polymerase 10 of 100～800 ℃ of conditions .5～10h acquisition complexing agent finished product; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5～10h obtains complexing agent finished product under 100～800 ℃ of conditions;
(2) preparation of electroplate liquid: the complexing agent of step (1) is dissolved in suitable quantity of water, then in proportion described mantoquita and zinc salt is dissolved in above-mentioned complexing agent aqueous solution, fill into again the water of surplus, then adjust pH to 8.5～9.5, obtain without cyanogen copper zinc alloy electroplate liquid.
The invention has the beneficial effects as follows:
(1) be of the present inventionly mixed into by complexing agent, mantoquita, zinc salt and water without cyanogen copper zinc alloy electroplate liquid, wherein the complex ability of complexing agent is strong, can reach 10 to the complexation constant of cupric ion
26be far superior to conventional complexing agent of the prior art, the stability of the electroplate liquid being made by this complexing agent improves greatly, the quality of electroplate liquid is high, this cyanideless electro-plating liquid when the preplating, the main salt metal ion in electroplate liquid not can with metal base generation replacement(metathesis)reaction, can not produce loose displacement layer structure, therefore, the bonding force of electrolytic coating and metal base is strong and coating surface is level and smooth, and the quality of electrolytic coating is greatly improved.
(2) this can electroplate without cyanogen copper zinc alloy electroplate liquid under the technological temperature of normal temperature to 65 ℃, and the speed of deposition coating can meet the needs of actual production, has improved the production efficiency of electroplating.
(3) of the present invention without cyanogen copper zinc alloy electroplate liquid at compared with high technology temperature time the dispersive ability of plating solution and the bonding force of coating significantly strengthen, and because the component of this electroplate liquid is not volatile, the composition of electroplate liquid is stable, the coating densification obtaining, the smooth surface of coating, has avoided in the electroplate liquid of prior art component volatile unsettled deficiency of electroplate liquid quality that causes at compared with high technology temperature.
(4) of the present invention can well be combined with metal base without cyanogen copper zinc alloy electroplate liquid, to metal base non-corrosiveness, applied range.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail.
Reagent in following each embodiment or raw material are all commercial conventional raw material, and purity is analytical pure, and the percentage ratio in each embodiment is mass percent.
Embodiment 1:
Without a preparation method for cyanogen copper zinc alloy electroplate liquid, described preparation method comprises the following steps:
(1) preparation of complexing agent: the general formula of described complexing agent is M
xh
yp
no
3n+ 1R
z, wherein x=3, y=0, n=2, z=1, M is K
+, R is ethanoyl, concrete structure formula is as follows:
By potassium hydroxide, phosphoric acid and acetic acid 3:2:1 hybrid reaction in molar ratio, reaction solution is dried and is obtained partially polymerized intermediate powder by spraying, this intermediate powder is placed in to rake type drier interior in 250 ℃ of polyreaction 10h, polyreaction finishes rear acquisition complexing agent finished product;
(2) preparation of mantoquita: the complexing agent that step (1) makes and copper sulfate in molar ratio 2:3 mix in aqueous phase system, in 25 ℃ of reaction 1h, after reaction finishes, through centrifugation the dry mantoquita that to obtain, the structural formula of mantoquita is as follows;
(3) preparation of zinc salt: the complexing agent that step (1) makes and zinc sulfate in molar ratio 2:3 mix in aqueous phase system, in 25 ℃ of reaction 1h, after reaction finishes, through centrifugation the dry zinc salt that to obtain, the structural formula of zinc salt is as follows;
(4) preparation of electroplate liquid: the complexing agent of 1.0% step (1) is dissolved in 50% water, then the zinc salt of the step (3) of the mantoquita of 0.01% step (2) and 0.01% is added in enveloping agent solution, adding 48.98% water mixes again, then use potassium hydroxide adjust pH to 8.5, obtain without cyanogen copper zinc alloy electroplate liquid.
Embodiment 2:
Without a preparation method for cyanogen copper zinc alloy electroplate liquid, described preparation method comprises the following steps:
(1) complexing agent preparation: the general formula of described complexing agent is M
xh
yp
no
3n+ 1R
z, wherein x=3, y=0, n=3, z=2, M is K
+and Na
+, R is ethanoyl, concrete structure formula is as follows:
By sodium hydroxide, phosphoric acid and acetic acid 3:3:2 hybrid reaction in molar ratio, reaction solution obtains partially polymerized intermediate powder by expansion drying, this intermediate powder is placed in to rake type drier interior in 200 ℃ of polyreaction 10h, polyreaction finishes rear acquisition complexing agent finished product;
(2) preparation of mantoquita: the complexing agent that step (1) makes and copper sulfate in molar ratio 2:3 mix in aqueous phase system, in 100 ℃ of reaction 0.5h, after reaction finishes, through centrifugation the dry mantoquita that to obtain, the structural formula of mantoquita is as follows;
(3) preparation of zinc salt: the complexing agent that step (1) makes and zinc sulfate in molar ratio 2:3 mix in aqueous phase system, in 100 ℃ of reaction 0.5h, after reaction finishes, through centrifugation the dry zinc salt that to obtain, the structural formula of zinc salt is as follows;
(4) preparation of electroplate liquid: the complexing agent of 30.0% step (1) is dissolved in 40% water, then the zinc salt of the mantoquita of 10% step (2) and 10% step (3) is dissolved in enveloping agent solution, adding 10.0% water mixes again, then adjust pH to 8.8, obtains without cyanogen copper zinc alloy electroplate liquid.
Embodiment 3:
Without a preparation method for cyanogen copper zinc alloy electroplate liquid, described preparation method comprises the following steps:
(1) complexing agent preparation: the general formula of described complexing agent is M
xh
yp
no
3n+ 1R
z, wherein x=1, y=100, n=100, z=1, M is Na
+, R is ethanoyl, concrete structure formula is as follows:
By sodium bicarbonate, phosphoric acid and acetic acid 1:100:1 hybrid reaction in molar ratio, reaction solution obtains partially polymerized intermediate powder by expansion drying, this intermediate powder is placed in to rake type drier interior in 300 ℃ of polyreaction 2.5h, polyreaction finishes rear acquisition complexing agent finished product;
(2) preparation of mantoquita: the complexing agent that step (1) is made and copper sulfate in molar ratio 2:1 mix, in 25 ℃ of reaction 1.0h, after reaction finishes, through centrifugation the dry mantoquita that to obtain, the structural formula of this mantoquita is as follows;
(3) preparation of zinc salt: the complexing agent that step (1) is made and zinc sulfate in molar ratio 2:1 mix, in 25 ℃ of reaction 1.0h, after reaction finishes, through centrifugation the dry zinc salt that to obtain, the structural formula of this zinc salt is as follows;
(4) preparation of electroplate liquid: the complexing agent of 40.0% step (1) is dissolved in 30% water, then the zinc salt of the mantoquita of 5.0% step (2) and 5.0% step (3) is dissolved in enveloping agent solution, adding 20.0% water mixes again, then adjust pH to 8.7, obtains without cyanogen copper zinc alloy electroplate liquid.
Embodiment 4:
Without a preparation method for cyanogen copper zinc alloy electroplate liquid, described preparation method comprises the following steps:
(1) complexing agent preparation: the general formula of described complexing agent is M
xh
yp
no
3n+ 1R
z, wherein x=1, y=100, n=100, z=1, M is Na
+, R is the amide group forming after ala dehydratase, concrete structure formula is as follows:
By sodium bicarbonate, phosphoric acid and L-Ala 1:100:1 hybrid reaction in molar ratio, reaction solution obtains partially polymerized intermediate powder by expansion drying, this intermediate powder is placed in to rake type drier interior in 300 ℃ of polyreaction 2.5h, polyreaction finishes rear acquisition complexing agent finished product;
(2) preparation of mantoquita: the complexing agent that step (1) is made and copper sulfate in molar ratio 2:1 mix, in 25 ℃ of reaction 1.0h, after reaction finishes, through centrifugation the dry mantoquita that to obtain, the structural formula of this mantoquita is as follows;
(3) preparation of zinc salt: the complexing agent that step (1) is made and zinc sulfate in molar ratio 2:1 mix, in 25 ℃ of reaction 1.0h, after reaction finishes, through centrifugation the dry zinc salt that to obtain, the structural formula of this zinc salt is as follows;
(4) preparation of electroplate liquid: the complexing agent of 60.0% step (1) is dissolved in 20% water, then the zinc salt of the mantoquita of 0.5% step (2) and 0.5% step (3) is dissolved in enveloping agent solution, adding 19.0% water mixes again, then adjust pH to 8.5, obtains without cyanogen copper zinc alloy electroplate liquid.
Embodiment 5:
Without a preparation method for cyanogen copper zinc alloy electroplate liquid, described preparation method comprises the following steps:
(1) complexing agent preparation, the general formula of described complexing agent is M
xh
yp
no
3n+ 1R
z, wherein x=3, y=0, n=2, z=1, M is Na
+, R is the methyl that methyl acid phosphate dehydration has formation, concrete structure formula is as follows:
By sodium hydroxide, phosphoric acid and methyl acid phosphate 3:2:1 hybrid reaction in molar ratio, reaction solution obtains partially polymerized intermediate powder by expansion drying, this intermediate powder is placed in to rake type drier interior in 300 ℃ of polyreaction 5h, polyreaction finishes rear acquisition complexing agent finished product;
(2) preparation of mantoquita: the complexing agent that step (1) is made and copper sulfate in molar ratio 2:3 mix, in the anti-1.0h of normal temperature, after reaction finishes, through centrifugation the dry mantoquita that to obtain, the structural formula of this mantoquita is as follows;
(3) preparation of zinc salt: the complexing agent that step (1) is made and zinc sulfate in molar ratio 2:3 mix, in the anti-1.0h of normal temperature, after reaction finishes, through centrifugation the dry zinc salt that to obtain, the structural formula of this zinc salt is as follows;
(4) preparation of electroplate liquid: the complexing agent of 40.0% step (1) is dissolved in 20% water, then the zinc salt of the mantoquita of 0.5% step (2) and 0.2% step (2) is dissolved in enveloping agent solution, adding 39.3% water mixes again, then adjust pH to 9.5, obtains without cyanogen copper zinc alloy electroplate liquid.
In preparation method without cyanogen copper zinc alloy electroplate liquid of the present invention, in embodiment 1 to 5 complexing agent used, complexing agent can also be the complexing agent as shown in embodiment 6～8, the complexing agent that embodiment 6～8 makes first generates mantoquita and zinc salt with cupric compound and zn cpds by certain molar ratio reaction respectively, and then mix in proportion with complexing agent, water, adjust pH to 8.5～9.5, obtain electroplate liquid of the present invention.
Embodiment 6:
A kind of complexing agent, the general formula of described complexing agent is M
xh
yp
no
3n+ 1R
z, wherein x=5, y=0, n=5, z=2, M is Na
+, R is the acyl group forming after ethanoyl and sodium hydrotartrate dehydration, concrete structure formula is as follows:
The preparation method of this complexing agent is as follows: by sodium bicarbonate, phosphoric acid, acetic acid and sodium hydrotartrate 5:5:1:1 hybrid reaction in molar ratio, then reaction solution obtains partially polymerized intermediate powder by expansion drying, this intermediate powder is placed in to rake type drier interior in 400 ℃ of polyreaction 0.5h, polyreaction finishes rear acquisition complexing agent finished product.
Embodiment 7:
A kind of complexing agent, the general formula of described complexing agent is M
xh
yp
no
3n+ 1R
z, wherein x=10, y=1, n=10, z=1, M is K
+and Na
+, R is the acyl group forming after sodium hydrotartrate dehydration, concrete structure formula is as follows:
The preparation method of this complexing agent is as follows: by sodium hydroxide, potassium hydroxide, phosphoric acid and sodium hydrotartrate 1:9:10:1 hybrid reaction in molar ratio, reaction solution is dried and is obtained partially polymerized intermediate powder by spraying, this intermediate powder is placed in to rake type drier interior in 800 ℃ of polyreaction 0.5h, polyreaction finishes rear acquisition complexing agent finished product.
Embodiment 8:
A kind of complexing agent, the general formula of described complexing agent is M
xh
yp
no
3n+ 1R
z, wherein x=10, y=1, n=10, z=1, M is Na
+, R is the acyl group forming after Monobasic sodium citrate dehydration, concrete structure formula is as follows:
The preparation method of this complexing agent is as follows: by sodium carbonate, phosphoric acid and Monobasic sodium citrate 5:10:1 hybrid reaction in molar ratio, reaction solution obtains partially polymerized intermediate powder by expansion drying, this intermediate powder is placed in to rake type drier interior in 400 ℃ of polyreaction 0.5h, polyreaction finishes rear acquisition complexing agent finished product.
The copper zinc alloy electroplate liquid that embodiment 1 to 5 is made has carried out following research:
1, Hull groove test (267ml)
1.1 tentative experiments: the electroplate liquid respectively embodiment 1 to embodiment 5 being made is 25 ℃ of temperature, circuit 1A(current stabilization), the lower sheet of beating of condition of pneumatic blending, time 5min, beat in sheet process and observe under current stabilization condition, groove presses also relatively stable and plating sheet in larger area, to show half luminous point, the careful feature of crystal.
Current density range is determined in the test of 1.2Hull groove:
The electroplate liquid making with embodiment 1 to embodiment 5 is respectively 55 ℃ of temperature, electric current 1A, and time 10min, beats sheet by Hull and determines optimum current density range, breaks sheet material that sheet selects and adopt the A3 steel disc of 0.5*70*100,600# silicon carbide paper sanding and polishing.With reference to experimental formula J
k=I(5.1-5.24LgL) calculate the current density of test piece every bit.Calculate and can draw by beating sheet and current density, the current density range of the electroplate liquid that embodiment 1 to embodiment 5 makes is 0.5A/dm
2to 2.5A/dm
2between.
2 electroplate liquids and plating performance test
The mensuration of 2.1 current efficiency: adopt copper voltameter to measure, the current efficiency of the electroplate liquid that embodiment 1 makes is 93.1%, the current efficiency of the electroplate liquid that embodiment 2 makes is 92.8%, the current efficiency of the electroplate liquid that embodiment 3 makes is 93.2%, the current efficiency of the electroplate liquid that embodiment 4 makes is that the current efficiency of the electroplate liquid that makes of 93.5%, embodiment 5 is 93.4%.
2.2 electroplate liquid dispersive abilities are measured
The dispersive ability of surveying electroplate liquid by bending cathode method, condition is electric current 1A, oil-free air stirs, 55 ℃ of temperature, time 30min, examination material is selected the A3 copper sheet of 0.5*70*100,600# silicon carbide paper sanding and polishing.
The dispersive ability of the electroplate liquid of the embodiment 1 recording is 93.2%, the dispersive ability of the electroplate liquid of the embodiment 2 recording is 92.8%, the dispersive ability of the electroplate liquid of the embodiment 3 recording is 93.0%, the dispersive ability of the electroplate liquid of embodiment 4 is that the dispersive ability of the electroplate liquid of 93.0%, embodiment 5 is 93.1%.
The mensuration of 2.3 covering powers
Adopt endoporus method to measure the covering power of plating solution, copper pipe size 10mm*100mm, adopts through hole and Blind Hole Method, and temperature of electroplating solution is 55 ℃, and cathode current density is 0.5A/dm
2, time 5min.After experiment, cut iron pipe open, coating situation in observation tube.
Take the electroplate liquid of embodiment 1 to 5 as experiment electroplate liquid, after experiment, find that through hole and blind hole have all plated copper zinc alloy layer respectively, illustrate that the covering power of the electroplate liquid that embodiment 1 to embodiment 5 makes is good.
2.4 bonding force tests
2.4.1 crooked experiment: adopt the polishing iron plate (A3) that thickness is 0.5mm, the temperature of electroplate liquid is 55 ℃, and cathode current density is 2A/dm
2, time 15min.
Respectively take the electroplate liquid of embodiment 1 to 5 as experiment electroplate liquid, after experiment by the test piece alternating bending of plate to rupturing, breach place, without the phenomenon of peeling, proves that coating does not separate with matrix.2.4.2 thermal shock experiment: adopt the polishing iron plate (A3) that thickness is 0.5mm, the temperature of electroplate liquid is 55 ℃, and cathode current density is 2A/dm
2, time 15min.
Take the electroplate liquid of embodiment 1 to 5 as experiment electroplate liquid, after experiment, the test piece of plate is placed in baking oven and is baked to 200 ℃ respectively, toast continuously 1h, immerse immediately quenching in 0 ℃ of water after taking-up, result is not found coating foaming and the phenomenon of peeling.
2.5 ductility of electrodeposited film experiments: by A3 steel disc chromic acid passivation thick 1mm, be hung in the electroplate liquid of embodiment 1 to 5 after cleaning, the thickness of coating reaches after 20 μ m, coating is stripped down, bending 180 ℃, and push knee, coating does not rupture, and shows that ductility of electrodeposited film is good.
2.6 coating porosity experiments: adopt the polishing iron plate (A3) that thickness is 0.5mm, 55 ℃ of the temperature of electroplate liquid, cathode current density 1A/dm
2, time 20min, pastes filter paper laboratory method with potassium ferricyanide solution and carries out porosity experiment.
Tripotassium iron hexacyanide 10g/L; Sodium-chlor 20g/L.
Experimental result shows, the porosity of the electrolytic coating that the electroplate liquid that embodiment 1 to embodiment 5 makes forms as experimental subjects all≤1/dm
2.
The mensuration of 2.7 sedimentation velocities: set electric current 1A, 55 ℃ of temperature, time 30min, measurement result shows, the sedimentation velocity of the electroplate liquid that embodiment 1 makes is 0.6 μ m/min, and the sedimentation velocity of the electroplate liquid that embodiment 2 makes is 0.62 μ m/min, and the sedimentation velocity of the electroplate liquid that embodiment 3 makes is 0.56 μ m/min, the sedimentation velocity of the electroplate liquid that embodiment 4 makes is 0.52 μ m/min, and the sedimentation velocity of the electroplate liquid that embodiment 5 makes is 0.55 μ m/min.
The electroplate liquid that embodiment 1 to embodiment 5 is made further carries out respectively pilot experiment, and pilot process parameter is as follows:
Technical process: electroplate liquid → recovery → washing 1 → washing 2 → acid activation → sour copper of iron and steel parts → ultrasonic wave oil removing → washing 1 → washing 2 → anode electrolysis oil removing → washing 1 → washing 2 → pickling degreasing → washing 1 → washing 2 → salt pickling → washing 1 → washing 2 → terminal electrolytic degreasing → washing 1 → washing 2 → acid activation → washing 1 → washing 2 → embodiment 1 to 5.
Ultrasonic wave oil removing: degreasing powder concentration 50 ± 5g/L, 70 ± 5 ℃ of temperature, current density 1-5A/dm2,5 minutes time.
Catholyte oil removing: electrolytic degreasing powder concentration 50 ± 5g/L, 70 ± 5 ℃ of temperature, current density 1-5A/dm2,5～7 minutes time.
Anode electrolysis oil removing: electrolytic degreasing powder concentration 50 ± 5g/L, 70 ± 5 ℃ of temperature, current density 1-5A/dm
2, 3～5 minutes time.
Pickling: technical hydrochloric acid concentration 15～20%, time 8～10min, room temperature.
Activation: technical hydrochloric acid concentration 5～10%, time 3～5min, room temperature.
The electroplate liquid of embodiment 1 to 5: degree Beaume 32-36, pH value 8.5～9.5,50～55 ℃ of temperature, current density 0.5～2.5A/dm
2, time 5min to a few hours not etc., facts have proved, be plating to 100 μ m leveling property, luminance brightness is also very good.
Move 20 months continuously by 50L pilot scale electroplating assembly line, 350L pilot scale electroplating assembly line moves 11 months continuously, has verified that the electroplate liquid that embodiment 1 to 5 makes has reliability, and plating solution performance is stable, and the consumption of plating solution is 10～50ml/KAH.
On the experiment basis of above-mentioned pilot scale, the electroplate liquid that acquisition embodiment 1 to 5 makes is for the processing condition of suitability for industrialized production.
1, iron and steel parts:
Technical process: electroplate liquid → recovery → washing 1 → washing 2 → acid activation → sour copper of iron and steel parts → ultrasonic wave oil removing → washing 1 → washing 2 → anode electrolysis oil removing → washing 1 → washing 2 → pickling degreasing → washing 1 → washing 2 → salt pickling → washing 1 → washing 2 → terminal electrolytic degreasing → washing 1 → washing 2 → acid activation → washing 1 → washing 2 → preimpregnation → embodiment 1 to 5.
Processing condition:
Electroplate liquid density: 32～36 degree Beaume
45～65 ℃ of temperature
PH value: 8.60～9.50
Stir: pneumatic blending adds movable cathode
Anode: electrolytic copper or anaerobic electrolytic copper
Negative and positive Area Ratio: 1:1.5～2.
Electric current: 0.5～2.5A/dm
2.
2, zinc alloy workpiece:
The electroplate liquid of technical process: zinc alloy workpiece → hot dipping paraffin removal → ultrasonic wave paraffin removal → washing 1 → washing 2 → ultrasonic wave oil removing → washing 1 → washing 2 → anode electrolysis oil removing → washing 1 → washing 2 → acid salt activating → washing 1 → washing 2 → ultrasonic wave presoak preimpregnation 30s → embodiment 1 to 5 (charged enter groove 25～35 ℃) → reclaim → washing 1 → washing 2 → acid activation → sour copper.
Processing condition:
Electroplate liquid density: 32～38 degree Beaume
25～35 ℃ of temperature
PH value: 8.60～9.50
Stir: pneumatic blending adds movable cathode
Anode: electrolytic copper or anaerobic electrolytic copper
Negative and positive Area Ratio: 1:1.5～2.
Electric current: 0.5～1.5A/dm
2.
Above-described embodiment is preferably scheme of one of the present invention, not the present invention is done to any pro forma restriction, also has other variant and remodeling under the prerequisite that does not exceed the technical scheme that claim records.
Above-described embodiment is preferably scheme of one of the present invention, not the present invention is done to any pro forma restriction, also has other variant and remodeling under the prerequisite that does not exceed the technical scheme that claim records.
Claims (8)
1. without a cyanogen copper zinc alloy electroplate liquid, it is characterized in that: described electroplate liquid is made up of the component of following weight percent: complexing agent 1～60%, mantoquita 0.01～10%, zinc salt 0.01～10%, surplus is water, the general formula of described complexing agent is M
xh
yp
no
3n+1r
z, wherein M be in alkalimetal ion and NH4+ any one or multiple, R is acyl group, the general formula of mantoquita is Cu
x/2h
yp
no
3n+1r
z, the general formula of zinc salt is Zn
x/2h
yp
no
3n+1r
z, described x, n and z are positive integer, and y is 0 or positive integer, x+y+z=n+2.
2. one according to claim 1 is without cyanogen copper zinc alloy electroplate liquid, it is characterized in that: described electroplate liquid is made up of the component of following weight percent: complexing agent 20～45%, mantoquita 0.5～10.0%, zinc salt 0.2～5.0%, surplus is water, and the general formula of described complexing agent is M
xh
yp
no
3n+1r, wherein M is Na
+, K
+with in NH4+ any one or multiple, R is acyl group, the general formula of mantoquita is Cu
x/2h
yp
no
3n+1r, the general formula of zinc salt is Zn
x/2h
yp
no
3n+1r, described x and n are positive integer, and y is 0 or positive integer, x+y=n+1.
3. the preparation method without cyanogen copper zinc alloy electroplate liquid described in claim 1 or 2, is characterized in that: the preparation method of described electroplate liquid is as follows:
(1) preparation of complexing agent: by containing alkali, carbonate or the supercarbonate of M with phosphoric acid, containing the monobasic organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution is at next step polymerase 10 of 100～800 ℃ of conditions .5～10h acquisition complexing agent finished product; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5～10h obtains complexing agent finished product under 100～800 ℃ of conditions;
(2) preparation of mantoquita: the complexing agent that step (1) is made mixes in molar ratio with cupric compound in aqueous phase system, in 25～100 ℃ of reaction 0.5～1h, is also dried and obtains mantoquita through centrifugation after reaction finishes;
(3) preparation of zinc salt: the complexing agent that step (1) is made mixes in molar ratio with divalent zinc compound in aqueous phase system, in 25～100 ℃ of reaction 0.5～1h, is also dried and obtains zinc salt through centrifugation after reaction finishes;
(4) preparation of electroplate liquid: the complexing agent of step (1) is dissolved in suitable quantity of water, then in proportion the zinc salt of the mantoquita of step (2) and step (3) is dissolved in above-mentioned complexing agent aqueous solution, the water that fills into again surplus mixes, then adjust pH to 8.5～9.5, obtain without cyanogen copper zinc alloy electroplate liquid.
4. the preparation method without cyanogen copper zinc alloy electroplate liquid according to claim 3, is characterized in that, it is characterized in that, when M is Na
+time, the preparation manipulation of complexing agent is as follows in step (1): by sodium hydroxide, sodium carbonate or sodium bicarbonate, with phosphoric acid, containing the monobasic organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution is at next step polymerase 10 of 200～400 ℃ of conditions .5～10h acquisition complexing agent finished product; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5～10h obtains complexing agent finished product under 200～400 ℃ of conditions.
5. the preparation method without cyanogen copper zinc alloy electroplate liquid according to claim 3, is characterized in that, when M is K
+time, the preparation manipulation of complexing agent is as follows in step (1): by potassium hydroxide, salt of wormwood or saleratus, with phosphoric acid, containing the monobasic organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution is at next step polymerase 10 of 250～800 ℃ of conditions .5～10h acquisition complexing agent finished product; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5～10h obtains complexing agent finished product under 250～800 ℃ of conditions.
6. the preparation method without cyanogen copper zinc alloy electroplate liquid according to claim 3, it is characterized in that, in the time that M is NH4+, the preparation manipulation of complexing agent is as follows in step (1): by ammoniacal liquor, volatile salt or bicarbonate of ammonia, with phosphoric acid, containing the monobasic organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution is at next step polymerase 10 of 100～300 ℃ of conditions .5～10h acquisition complexing agent finished product; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5～10h obtains complexing agent finished product under 100～300 ℃ of conditions.
7. one according to claim 1 and 2 is without cyanogen copper zinc alloy electroplate liquid, it is characterized in that, described mantoquita can also directly be selected from any one or a few in copper sulfate, cupric chloride or ventilation breather, and described zinc salt can also be selected from any one or a few in zinc sulfate, zinc chloride or zinc subcarbonate.
8. the preparation method without cyanogen copper zinc alloy electroplate liquid claimed in claim 7, is characterized in that, described preparation method is as follows:
(1) preparation of complexing agent: by containing alkali, carbonate or the supercarbonate of M with phosphoric acid, containing the monobasic organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution is at next step polymerase 10 of 100～800 ℃ of conditions .5～10h acquisition complexing agent finished product; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5～10h obtains complexing agent finished product under 100～800 ℃ of conditions;
(2) preparation of electroplate liquid: the complexing agent of step (1) is dissolved in suitable quantity of water, then in proportion mantoquita claimed in claim 7 and zinc salt is dissolved in above-mentioned complexing agent aqueous solution, fill into again the water of surplus, then adjust pH to 8.5～9.5, obtain without cyanogen copper zinc alloy electroplate liquid.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105132973A (en) * | 2015-09-22 | 2015-12-09 | 太原工业学院 | Environment-friendly type non-cyanide electroplating copper-zinc alloy solution and electroplating copper-zinc alloy process thereof |
| CN108203837A (en) * | 2018-04-04 | 2018-06-26 | 临海市伟星电镀有限公司 | A kind of no cyamelide copper and tin electroplate liquid and its preparation method |
| CN109853008A (en) * | 2018-06-07 | 2019-06-07 | 临海市伟星电镀有限公司 | A kind of no cyanogen brass electroplating liquid and preparation method thereof |
| CN110965089A (en) * | 2019-12-23 | 2020-04-07 | 黄河水利职业技术学院 | Metal electroplating liquid, preparation and use method |
| CN113668027A (en) * | 2021-07-29 | 2021-11-19 | 江苏兴达钢帘线股份有限公司 | Method for manufacturing brass plating layer steel wire, tire bead steel wire, rubber tube steel wire and steel cord |
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| CN102051648A (en) * | 2011-01-20 | 2011-05-11 | 广州市二轻工业科学技术研究所 | Cyanogen-free plating method of zinc alloy die casting |
| CN102978627A (en) * | 2012-11-01 | 2013-03-20 | 西南大学 | Method for preparing super-hydrophobic surface on magnesium alloy |
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2014
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051648A (en) * | 2011-01-20 | 2011-05-11 | 广州市二轻工业科学技术研究所 | Cyanogen-free plating method of zinc alloy die casting |
| CN102978627A (en) * | 2012-11-01 | 2013-03-20 | 西南大学 | Method for preparing super-hydrophobic surface on magnesium alloy |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105132973A (en) * | 2015-09-22 | 2015-12-09 | 太原工业学院 | Environment-friendly type non-cyanide electroplating copper-zinc alloy solution and electroplating copper-zinc alloy process thereof |
| CN108203837A (en) * | 2018-04-04 | 2018-06-26 | 临海市伟星电镀有限公司 | A kind of no cyamelide copper and tin electroplate liquid and its preparation method |
| CN109853008A (en) * | 2018-06-07 | 2019-06-07 | 临海市伟星电镀有限公司 | A kind of no cyanogen brass electroplating liquid and preparation method thereof |
| CN110965089A (en) * | 2019-12-23 | 2020-04-07 | 黄河水利职业技术学院 | Metal electroplating liquid, preparation and use method |
| CN113668027A (en) * | 2021-07-29 | 2021-11-19 | 江苏兴达钢帘线股份有限公司 | Method for manufacturing brass plating layer steel wire, tire bead steel wire, rubber tube steel wire and steel cord |
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|---|---|
| CN103806041B (en) | 2016-04-27 |
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