CN103806041B - A kind of without cyanogen copper zinc alloy electroplate liquid and preparation method thereof - Google Patents
A kind of without cyanogen copper zinc alloy electroplate liquid and preparation method thereof Download PDFInfo
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- CN103806041B CN103806041B CN201410014014.9A CN201410014014A CN103806041B CN 103806041 B CN103806041 B CN 103806041B CN 201410014014 A CN201410014014 A CN 201410014014A CN 103806041 B CN103806041 B CN 103806041B
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Abstract
The present invention relates to a kind of without cyanogen copper zinc alloy electroplate liquid and preparation method thereof, described electroplate liquid is made up of the component of following weight percents: complexing agent 1 ~ 60%, mantoquita 0.3 ~ 10%, zinc salt 0.2 ~ 10%, and surplus is water, and the general formula of described complexing agent is M
xh
yp
no
3n+1r
z, wherein M is alkalimetal ion and NH
4+in any one or multiple, R is acyl group, and 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.Of the present inventionly be mixed into by complexing agent, mantoquita, zinc salt and water without cyanogen copper zinc alloy electroplate liquid, the complex ability of its 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 obtained by this complexing agent improves greatly, the quality of electroplate liquid is high, when this cyanideless electro-plating liquid is used for preplating, main salt metal ion in electroplate liquid can not with metal base generation replacement(metathesis)reaction, can not produce loose displacement layer structure, the quality of electrolytic coating is greatly improved.
Description
Technical field
The present invention relates to a kind of electroplate liquid, relate to a kind of without cyanogen copper zinc alloy electroplate liquid and preparation method thereof specifically, belong to Cu electroplating zinc technical field.
Background technology
Copper zinc alloy coating has flavous outward appearance, but also chemical stain can be carried out in its surface, to reach special decorative effect, therefore, be widely used in decorative coating, but because the standard potential difference of copper, zinc is comparatively large, therefore desirable alloy layer can not be obtained from single salts solution, still there is no a kind of electroplate liquid of replacement cyanide electroplating zinc alloy that can be satisfied so far.
Although the copper zinc coating adopting the copper zinc alloy electroplate liquid (i.e. cupric cyanide zinc electroplate liquid) containing prussiate to obtain is careful, bonding force good, and all platings of electroplate liquid, Surface flat and stability are also very good.But prussiate is severe poisonous chemicals, it is only 0.005g to the lethal quantity of people, and prussiate had both endangered the healthy of operator, simultaneously contaminate environment again, and waste water is difficult to administer, and its sewage disposal expense is high.Therefore in order to protection of the environment, reduce public hazards, urgently exploitation is a kind of without cyanogen copper zinc electroplate liquid.
Summary of the invention
The object of the invention is to solve the cupric cyanide zinc electroplate liquid of prior art containing toxic substance cyanogen, affect operator healthy, contaminate environment, and the reluctant deficiency of its waste water, there is provided a kind of not containing the copper zinc alloy electroplate liquid of cyanogen, this electroplate liquid is not containing cyanogen, and environmental friendliness, manufactures, to store 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 percents: complexing agent 1 ~ 60%, mantoquita 0.01 ~ 10%, zinc salt 0.01 ~ 10%, surplus is water, and 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, and 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 example to explain the structure of above-mentioned component complexing agent:
A: work as x=1, during y=1, z=n, the general formula of complexing agent is MHP
no
3n+1r
n, its structural formula as the formula (1):
structural formula (1);
B: work as x=n, during y=0, z=2 is M while complexing agent
np
no
3n+1r
2, its structural formula as the formula (2):
structural formula (2);
C: work as x=1, during 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):
structural formula (3)
Of the present inventionly be mixed into by complexing agent, mantoquita, zinc salt and water without cyanogen copper zinc alloy electroplate liquid, the complex ability of its 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 obtained by this complexing agent improves greatly, the quality of electroplate liquid is high, this cyanideless electro-plating liquid be used for preplating time, the main salt metal ion in electroplate liquid can not with metal base generation replacement(metathesis)reaction, loose displacement layer structure can not be produced, therefore, the bonding force of electrolytic coating and metal base is strong and coating surface 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 percents: complexing agent 20 ~ 45%, mantoquita 0.5 ~ 10.0%, zinc salt 0.2 ~ 5.0%, and 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, and 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 is positive integer, and y is 0 or positive integer, x+y=n+1.
Below with several example to explain the composition of the complexing agent in this optimal technical scheme:
D: as 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: as y=1, x=n, the general formula of complexing agent is M
nhP
no
3n+1r, its structural formula as the formula (5):
structural formula (5);
F: as 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):
structural 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 the alkali of M, carbonate or supercarbonate with phosphoric acid, containing the unitary organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution is at 100 ~ 800 DEG C of next step polymerase 10 of condition .5 ~ 10h acquisition complexing agent finished products; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5 ~ 10h obtains complexing agent finished product under 100 ~ 800 DEG C of conditions;
(2) preparation of mantoquita: complexing agent obtained for step (1) is mixed in molar ratio with cupric compound in aqueous phase system, in 25 ~ 100 DEG C of reaction 0.5 ~ 1h, after reaction terminates through centrifugation and dry must mantoquita;
(3) preparation of zinc salt: complexing agent obtained for step (1) is mixed in molar ratio with divalent zinc compound in aqueous phase system, in 25 ~ 100 DEG C of reaction 0.5 ~ 1h, after reaction terminates through centrifugation and dry must zinc salt;
(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 filling into surplus again 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 is high, drying mode in step (1) is spraying 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 is close to 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 step (1) complexing agent is as follows: by sodium hydroxide, sodium carbonate or sodium bicarbonate and phosphoric acid, containing the unitary organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution obtains complexing agent finished product at 200 ~ 400 DEG C of next step polymerase 10 of condition .5 ~ 10h; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5 ~ 10h obtains complexing agent finished product under 200 ~ 400 DEG C of conditions.
As preferably, when M is K
+time, the preparation manipulation of step (1) complexing agent is as follows: by potassium hydroxide, salt of wormwood or saleratus and phosphoric acid, containing the unitary organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution obtains complexing agent finished product at 250 ~ 800 DEG C of next step polymerase 10 of condition .5 ~ 10h; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5 ~ 10h obtains complexing agent finished product under 250 ~ 800 DEG C of conditions.
As preferably, when M is NH4+, the preparation manipulation of step (1) complexing agent is as follows: by ammoniacal liquor, volatile salt or bicarbonate of ammonia and phosphoric acid, containing the unitary organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution obtains complexing agent finished product at 100 ~ 300 DEG C of next step polymerase 10 of condition .5 ~ 10h; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5 ~ 10h obtains complexing agent finished product under 100 ~ 300 DEG C of conditions.
Except the mantoquita listed except above-mentioned, zinc salt, of the present invention without the mantoquita in cyanogen copper zinc alloy electroplate liquid can also directly be selected from copper sulfate, cupric chloride or ventilation breather any one or a few, zinc salt can also directly be selected from zinc sulfate, zinc chloride or zinc subcarbonate any one or a few, when 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 the alkali of M, carbonate or supercarbonate with phosphoric acid, containing the unitary organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution is at 100 ~ 800 DEG C of next step polymerase 10 of condition .5 ~ 10h acquisition complexing agent finished products; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5 ~ 10h obtains complexing agent finished product under 100 ~ 800 DEG C of conditions;
(2) preparation of electroplate liquid: the complexing agent of step (1) is dissolved in and in proportion described mantoquita and zinc salt is dissolved in above-mentioned complexing agent aqueous solution in suitable quantity of water, then, fill into the water of surplus again, 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, the complex ability of its 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 obtained by this complexing agent improves greatly, the quality of electroplate liquid is high, this cyanideless electro-plating liquid be used for preplating time, the main salt metal ion in electroplate liquid can not with metal base generation replacement(metathesis)reaction, loose displacement layer structure can not be produced, therefore, the bonding force of electrolytic coating and metal base is strong and coating surface 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 DEG C, and the speed of deposited plating layer, can meet the needs of actual production, improves the production efficiency of plating.
(3) of the present inventionly significantly to strengthen without the dispersive ability of plating solution and the bonding force of coating when cyanogen copper zinc alloy electroplate liquid is at compared with high technology temperature, and due to the component of this electroplate liquid not volatile, the composition of electroplate liquid is stablized, the plated layer compact obtained, the smooth surface of coating, to avoid in the electroplate liquid of prior art component volatile deficiency causing electroplate liquid quality instability 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 convenient source, 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 are K
+, R is ethanoyl, and concrete structure formula is as follows:
By potassium hydroxide, phosphoric acid and acetic acid 3:2:1 hybrid reaction in molar ratio, reaction solution obtains partially polymerized intermediate powder by spraying dry, this intermediate powder be placed in 250 DEG C of polyreaction 10h in rake type drier, polyreaction terminates rear acquisition complexing agent finished product;
(2) preparation of mantoquita: the obtained complexing agent of step (1) and copper sulfate in molar ratio 2:3 mix in aqueous phase system, in 25 DEG C of reaction 1h, after reaction terminates through centrifugation and dry must mantoquita, the structural formula of mantoquita is as follows;
(3) preparation of zinc salt: the obtained complexing agent of step (1) and zinc sulfate in molar ratio 2:3 mix in aqueous phase system, in 25 DEG C of reaction 1h, after reaction terminates through centrifugation and dry must zinc salt, the structural formula of zinc salt is as follows;
(4) preparation of electroplate liquid: the complexing agent of the step (1) by 1.0% is dissolved in the water of 50%, then the zinc salt of the mantoquita of the step (2) of 0.01% and the step (3) of 0.01% is added in enveloping agent solution, the water adding 48.98% again mixes, 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 are K
+and Na
+, R is ethanoyl, and 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 be placed in 200 DEG C of polyreaction 10h in rake type drier, polyreaction terminates rear acquisition complexing agent finished product;
(2) preparation of mantoquita: the obtained complexing agent of step (1) and copper sulfate in molar ratio 2:3 mix in aqueous phase system, in 100 DEG C of reaction 0.5h, after reaction terminates through centrifugation and dry must mantoquita, the structural formula of mantoquita is as follows;
(3) preparation of zinc salt: the obtained complexing agent of step (1) and zinc sulfate in molar ratio 2:3 mix in aqueous phase system, in 100 DEG C of reaction 0.5h, after reaction terminates through centrifugation and dry must zinc salt, the structural formula of zinc salt is as follows;
(4) preparation of electroplate liquid: the complexing agent of the step (1) by 30.0% is dissolved in the water of 40%, then the mantoquita of the step (2) of 10% and the zinc salt of 10% step (3) are dissolved in enveloping agent solution, the water adding 10.0% again mixes, 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 are Na
+, R is ethanoyl, and 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 be placed in 300 DEG C of polyreaction 2.5h in rake type drier, polyreaction terminates rear acquisition complexing agent finished product;
(2) preparation of mantoquita: by complexing agent obtained for step (1) and copper sulfate in molar ratio 2:1 mix, in 25 DEG C of reaction 1.0h, after reaction terminates through centrifugation and dry must mantoquita, the structural formula of this mantoquita is as follows;
(3) preparation of zinc salt: by complexing agent obtained for step (1) and zinc sulfate in molar ratio 2:1 mix, in 25 DEG C of reaction 1.0h, after reaction terminates through centrifugation and dry must zinc salt, the structural formula of this zinc salt is as follows;
(4) preparation of electroplate liquid: the complexing agent of the step (1) by 40.0% is dissolved in the water of 30%, then the mantoquita of the step (2) of 5.0% and the zinc salt of 5.0% step (3) are dissolved in enveloping agent solution, the water adding 20.0% again mixes, 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 are Na
+, R is the amide group formed after ala dehydratase, and 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 be placed in 300 DEG C of polyreaction 2.5h in rake type drier, polyreaction terminates rear acquisition complexing agent finished product;
(2) preparation of mantoquita: by complexing agent obtained for step (1) and copper sulfate in molar ratio 2:1 mix, in 25 DEG C of reaction 1.0h, after reaction terminates through centrifugation and dry must mantoquita, the structural formula of this mantoquita is as follows;
(3) preparation of zinc salt: by complexing agent obtained for step (1) and zinc sulfate in molar ratio 2:1 mix, in 25 DEG C of reaction 1.0h, after reaction terminates through centrifugation and dry must zinc salt, the structural formula of this zinc salt is as follows;
(4) preparation of electroplate liquid: the complexing agent of the step (1) by 60.0% is dissolved in the water of 20%, then the mantoquita of the step (2) of 0.5% and the zinc salt of 0.5% step (3) are dissolved in enveloping agent solution, the water adding 19.0% again mixes, 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 are Na
+, R is the methyl that methyl acid phosphate dehydration has formation, and 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 be placed in 300 DEG C of polyreaction 5h in rake type drier, polyreaction terminates rear acquisition complexing agent finished product;
(2) preparation of mantoquita: by complexing agent obtained for step (1) and copper sulfate in molar ratio 2:3 mix, in the anti-1.0h of normal temperature, after reaction terminates through centrifugation and dry must mantoquita, the structural formula of this mantoquita is as follows;
(3) preparation of zinc salt: by complexing agent obtained for step (1) and zinc sulfate in molar ratio 2:3 mix, in the anti-1.0h of normal temperature, after reaction terminates through centrifugation and dry must zinc salt, the structural formula of this zinc salt is as follows;
(4) preparation of electroplate liquid: the complexing agent of the step (1) by 40.0% is dissolved in the water of 20%, then the mantoquita of the step (2) of 0.5% and the zinc salt of 0.2% step (2) are dissolved in enveloping agent solution, the water adding 39.3% again mixes, 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, except complexing agent used in embodiment 1 to 5, complexing agent can also be the complexing agent as shown in embodiment 6 ~ 8, the complexing agent that embodiment 6 ~ 8 obtains 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, namely 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 are Na
+, R is ethanoyl and the rear acyl group formed of sodium hydrotartrate dehydration, and 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 be placed in 400 DEG C of polyreaction 0.5h in rake type drier, polyreaction terminates 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 are K
+and Na
+, R is the acyl group formed after sodium hydrotartrate dehydration, and 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 obtains partially polymerized intermediate powder by spraying dry, this intermediate powder be placed in 800 DEG C of polyreaction 0.5h in rake type drier, polyreaction terminates 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 are Na
+, R is the acyl group formed after Monobasic sodium citrate dehydration, and 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 be placed in 400 DEG C of polyreaction 0.5h in rake type drier, polyreaction terminates rear acquisition complexing agent finished product.
The copper zinc alloy electroplate liquid obtained to embodiment 1 to 5 has carried out following research:
1, Hull groove test (267ml)
1.1 tentative experiments: respectively to the obtained electroplate liquid of embodiment 1 to embodiment 5 temperature 25 DEG C, circuit 1A(current stabilization), the condition of pneumatic blending is lower beats sheet, time 5min, beating in sheet process observes under current stabilization condition, and the also relatively stable and plating sheet of groove pressure shows the careful feature of half luminous point, crystal in larger area.
Current density range is determined in the test of 1.2Hull groove:
Respectively with the obtained electroplate liquid of embodiment 1 to embodiment 5 temperature 55 DEG C, electric current 1A, time 10min, beat sheet determination optimum current density range by Hull, makes the A3 steel disc of the sheet material employing 0.5*70*100 that sheet is selected, 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 can draw by beating sheet and current density, the current density range of the electroplate liquid that embodiment 1 to embodiment 5 is obtained 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 is obtained is 93.1%, the current efficiency of the electroplate liquid that embodiment 2 is obtained is 92.8%, the current efficiency of the electroplate liquid that embodiment 3 is obtained is 93.2%, the current efficiency of the electroplate liquid that embodiment 4 is obtained is 93.5%, and the current efficiency of the electroplate liquid that embodiment 5 is obtained is 93.4%.
2.2 electroplate liquid dispersive abilities measure
Survey the dispersive ability of electroplate liquid by bending cathode method, condition is electric current 1A, and oil-free air stirs, temperature 55 DEG C, time 30min, and the A3 copper sheet of 0.5*70*100 selected by examination material, 600# silicon carbide paper sanding and polishing.
The dispersive ability of the electroplate liquid of the embodiment 1 recorded is 93.2%, the dispersive ability of the electroplate liquid of the embodiment 2 recorded is 92.8%, the dispersive ability of the electroplate liquid of the embodiment 3 recorded is 93.0%, the dispersive ability of the electroplate liquid of embodiment 4 is 93.0%, and the dispersive ability of the electroplate liquid of embodiment 5 is 93.1%.
The mensuration of 2.3 covering powers
Adopt endoporus method to measure the covering power of plating solution, copper tube size 10mm*100mm, adopt through hole and Blind Hole Method, temperature of electroplating solution is 55 DEG C, and cathode current density is 0.5A/dm
2, time 5min.Iron pipe is cut open, coating conditions in observation tube after experiment.
Respectively with the electroplate liquid of embodiment 1 to 5 for experiment electroplate liquid, find after experiment that through hole and blind hole have all plated copper zinc alloy layer, illustrate that the covering power of the electroplate liquid that embodiment 1 to embodiment 5 obtains is good.
2.4 bonding force tests
2.4.1 crooked experiment: employing thickness is the polishing iron plate (A3) of 0.5mm, and the temperature of electroplate liquid is 55 DEG C, and cathode current density is 2A/dm
2, time 15min.
Respectively with the electroplate liquid of embodiment 1 to 5 for experiment electroplate liquid, after experiment will the test piece alternating bending that plate to rupturing, breach place, without phenomenon of peeling, proves that coating is not separated with matrix.2.4.2 thermal shock experiment: employing thickness is the polishing iron plate (A3) of 0.5mm, and the temperature of electroplate liquid is 55 DEG C, and cathode current density is 2A/dm
2, time 15min.
Respectively with the electroplate liquid of embodiment 1 to 5 for experiment electroplate liquid, after experiment, the test piece of plate is put and is baked to 200 DEG C in an oven, toast 1h continuously, after taking-up, immerse quenching in 0 DEG C of water immediately, result do not find coating foaming and peel phenomenon.
2.5 ductility of electrodeposited film experiments: by A3 steel disc chromic acid passivation thick for 1mm, be hung in after cleaning in the electroplate liquid of embodiment 1 to 5, after the thickness of coating reaches 20 μm, coating is stripped down, bending 180 DEG C, and extrude knee, coating does not rupture, and shows that ductility of electrodeposited film is good.
2.6 coating porosity experiments: employing thickness is the polishing iron plate (A3) of 0.5mm, the temperature of electroplate liquid 55 DEG C, 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 obtained electroplate liquid of embodiment 1 to embodiment 5 is formed as experimental subjects is equal≤and 1/dm
2.
The mensuration of 2.7 sedimentation velocities: setting electric current 1A, temperature 55 DEG C, time 30min, measurement result shows, the sedimentation velocity of the electroplate liquid that embodiment 1 is obtained is 0.6 μm/min, and the sedimentation velocity of the electroplate liquid that embodiment 2 is obtained is 0.62 μm/min, and the sedimentation velocity of the electroplate liquid that embodiment 3 is obtained is 0.56 μm/min, the sedimentation velocity of the electroplate liquid that embodiment 4 is obtained is 0.52 μm/min, and the sedimentation velocity of the electroplate liquid that embodiment 5 is obtained is 0.55 μm/min.
The electroplate liquid obtained to embodiment 1 to embodiment 5 carries out pilot experiment respectively further, 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 oil removal → 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 oil removal: degreasing powder concentration 50 ± 5g/L, temperature 70 ± 5 DEG C, current density 1-5A/dm2,5 minutes time.
Catholyte oil removing: electrolytic degreasing powder concentration 50 ± 5g/L, temperature 70 ± 5 DEG C, current density 1-5A/dm2,5 ~ 7 minutes time.
Anode electrolysis oil removing: electrolytic degreasing powder concentration 50 ± 5g/L, temperature 70 ± 5 DEG C, 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, temperature 50 ~ 55 DEG C, current density 0.5 ~ 2.5A/dm
2, time 5min to a few hours not etc., facts have proved, be plating to 100 μm of Surface flat, luminance brightness also very good.
Run 20 months continuously by 50L pilot scale electroplating assembly line, 350L pilot scale electroplating assembly line runs 11 months continuously, and the electroplate liquid demonstrating embodiment 1 to 5 obtained has reliability, and plating solution performance is stablized, and the consumption of plating solution is 10 ~ 50ml/KAH.
On the experiment basis of above-mentioned pilot scale, obtain the processing condition that the obtained electroplate liquid of embodiment 1 to 5 is used for 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 oil removal → 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
Temperature 45 ~ 65 DEG C
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:
Technical process: the electroplate liquid of zinc alloy workpiece → hot dipping paraffin removal → ultrasonic wave paraffin removal → washing 1 → washing 2 → ultrasonic oil removal → 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 DEG C) → recovery → wash 1 → wash 2 → acid activation → sour copper.
Processing condition:
Electroplate liquid density: 32 ~ 38 degree Beaume
Temperature 25 ~ 35 DEG C
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 one of the present invention preferably scheme, not does any pro forma restriction to the present invention, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.
Above-described embodiment is one of the present invention preferably scheme, not does any pro forma restriction to the present invention, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.
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 percents: complexing agent 1 ~ 60%, mantoquita 0.01 ~ 10%, zinc salt 0.01 ~ 10%, surplus is water, and the general formula of described complexing agent is M
xh
yp
no
3n+1r
z, wherein M is alkalimetal ion and NH
4 +in any one or multiple, R is acyl group, and 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;
The preparation method of described electroplate liquid is as follows:
(1) preparation of complexing agent: by the acid salt hybrid reaction in molar ratio of the alkali containing M, the carbonate containing M or supercarbonate and the phosphoric acid containing M and the unitary organic acid containing R base or the poly-basic organic acid containing R base, then reaction solution is at 100 ~ 800 DEG C of next step polymerase 10 of condition .5 ~ 10h acquisition complexing agent finished products; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5 ~ 10h obtains complexing agent finished product under 100 ~ 800 DEG C of conditions;
(2) preparation of mantoquita: complexing agent obtained for step (1) is mixed in molar ratio with cupric compound in aqueous phase system, in 25 ~ 100 DEG C of reaction 0.5 ~ 1h, after reaction terminates through centrifugation and dry must mantoquita;
(3) preparation of zinc salt: complexing agent obtained for step (1) is mixed in molar ratio with divalent zinc compound in aqueous phase system, in 25 ~ 100 DEG C of reaction 0.5 ~ 1h, after reaction terminates through centrifugation and dry must zinc salt;
(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 filling into surplus again mixes, then adjust pH to 8.5 ~ 9.5, obtain without cyanogen copper zinc alloy electroplate liquid.
2. according to claim 1 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 percents: 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
+and NH
4 +in any one or multiple, R is acyl group, and 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 is 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 the acid salt hybrid reaction in molar ratio of the alkali containing M, the carbonate containing M or supercarbonate and the phosphoric acid containing M and the unitary organic acid containing R base or the poly-basic organic acid containing R base, then reaction solution is at 100 ~ 800 DEG C of next step polymerase 10 of condition .5 ~ 10h acquisition complexing agent finished products; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5 ~ 10h obtains complexing agent finished product under 100 ~ 800 DEG C of conditions;
(2) preparation of mantoquita: complexing agent obtained for step (1) is mixed in molar ratio with cupric compound in aqueous phase system, in 25 ~ 100 DEG C of reaction 0.5 ~ 1h, after reaction terminates through centrifugation and dry must mantoquita;
(3) preparation of zinc salt: complexing agent obtained for step (1) is mixed in molar ratio with divalent zinc compound in aqueous phase system, in 25 ~ 100 DEG C of reaction 0.5 ~ 1h, after reaction terminates through centrifugation and dry must zinc salt;
(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 filling into surplus again 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 step (1) complexing agent is as follows: by the acid salt hybrid reaction in molar ratio of sodium hydroxide, sodium carbonate or sodium bicarbonate and phosphoric acid and the unitary organic acid containing R base or the poly-basic organic acid containing R base, then reaction solution obtains complexing agent finished products at 200 ~ 400 DEG C of next step polymerase 10 of condition .5 ~ 10h; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5 ~ 10h obtains complexing agent finished product under 200 ~ 400 DEG C 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 step (1) complexing agent is as follows: by the acid salt hybrid reaction in molar ratio of potassium hydroxide, salt of wormwood or saleratus and phosphoric acid and the unitary organic acid containing R base or the poly-basic organic acid containing R base, then reaction solution obtains complexing agent finished products at 250 ~ 800 DEG C of next step polymerase 10 of condition .5 ~ 10h; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5 ~ 10h obtains complexing agent finished product under 250 ~ 800 DEG C of conditions.
6. the preparation method without cyanogen copper zinc alloy electroplate liquid according to claim 3, is characterized in that, when M is NH
4 +time, the preparation manipulation of step (1) complexing agent is as follows: by the acid salt hybrid reaction in molar ratio of ammoniacal liquor, volatile salt or bicarbonate of ammonia and phosphoric acid and the unitary organic acid containing R base or the poly-basic organic acid containing R base, then reaction solution obtains complexing agent finished products at 100 ~ 300 DEG C of next step polymerase 10 of condition .5 ~ 10h; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5 ~ 10h obtains complexing agent finished product under 100 ~ 300 DEG C of conditions.
7. according to claim 1 and 2 a kind of without cyanogen copper zinc alloy electroplate liquid, it is characterized in that, described mantoquita be directly selected from copper sulfate, cupric chloride or ventilation breather any one or a few, described zinc salt be directly selected from zinc sulfate, zinc chloride or zinc subcarbonate any one or a few.
8. the preparation method without cyanogen copper zinc alloy electroplate liquid according to claim 7, is characterized in that, described preparation method is as follows:
(1) preparation of complexing agent: by the acid salt hybrid reaction in molar ratio of the alkali containing M, the carbonate containing M or supercarbonate and the phosphoric acid containing M and the unitary organic acid containing R base or the poly-basic organic acid containing R base, then reaction solution is at 100 ~ 800 DEG C of next step polymerase 10 of condition .5 ~ 10h acquisition complexing agent finished products; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5 ~ 10h obtains complexing agent finished product under 100 ~ 800 DEG C of conditions;
(2) preparation of electroplate liquid: the complexing agent of step (1) is dissolved in and in proportion mantoquita according to claim 7 and zinc salt is dissolved in above-mentioned complexing agent aqueous solution in suitable quantity of water, then, fill into the water of surplus again, then adjust pH to 8.5 ~ 9.5, obtain without cyanogen copper zinc alloy electroplate liquid.
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| 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 |
| CN116396264A (en) * | 2023-03-03 | 2023-07-07 | 山东惟普新能源有限公司 | Method for preparing fluoroethylene carbonate by solvent-free one-pot method |
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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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| 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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