CN105112898A - Surface treatment method for zinc alloy die casting - Google Patents
Surface treatment method for zinc alloy die casting Download PDFInfo
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Abstract
The invention discloses a surface treatment method for a zinc alloy die casting. The surface treatment method for the zinc alloy die casting includes the following steps that (1) wax removal is carried out on a zinc alloy die casting blank; (2) the zinc alloy die casting obtained after wax removal is washed with water; (3) the zinc alloy die casting washed with water in the former step is soaked in a degreaser solution so that grease on the surface can be removed; (4) washing is carried out, particularly, the degreased zinc alloy die casting is washed with water; (5) sulfuric acid activation is carried out, particularly, the washed zinc alloy die casting is soaked in a sulfuric acid solution to be activated; (6) the activated zinc alloy die casting is washed with water; (7) the washed zinc alloy die casting is soaked in a solution not containing cyanide, and an alloy layer is obtained; (8) the alloyed zinc alloy die casting is washed with water; and (9) subsequent electroplating or chemical plating is carried out. According to the cyanide-free chemical alloy treatment in the surface treatment method, the solution used does not contain cyanide, a power source is not needed, heating is not needed, operation is simple, and the finally formed alloy layer is compact.
Description
Technical field
The invention belongs to die casting field, particularly relate to a kind of zinc alloy diecasting surface treatment method.
Background technology
Cyanide copper plating is for a long time as Electroplating on Zinc Die Castings bottoming copper-plating technique, but prussiate toxicity is large, causing serious threat to operative employee's human and environment, cause cyanide copper plating and cleaner production to be runed counter to, is therefore the direction of Future Development without cyanogen process of surface treatment.
Non-cyanogen process technology is the product of national cleaner production demand for development, eliminate cyanide electroplating to a great extent to the harm of operator and environment, many researchers have paid many painstaking effort in the exploration and popularization of cyanogenless electroplating technology, have also made significant headway.
But with other matrix phase ratios, the electroplating technology of zinc alloy diecasting is complicated, and especially on zinc alloy diecasting, cyanideless electro-plating difficulty is larger, the reasons such as bonding force is bad.So the copper pre-plating of zinc alloy piece is still hydride systems at present.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide a kind of zinc alloy diecasting surface treatment method, can without the need to power supply, without the need to heating, simple to operate.
A kind of zinc alloy diecasting surface treatment method, the treating method comprises following steps:
(1) zinc alloy diecasting blank paraffin removal: be immersed in wax removing agent solution by zinc alloy diecasting blank, removes the wax of zinc alloy diecasting blank surface, obtains the zinc alloy diecasting after paraffin removal; The BH-20 wax removing agent solution of described cerate solution to be concentration be 30 ~ 50ml/L;
(2) wash: the zinc alloy diecasting after paraffin removal is washed, removes the wax removing agent solution of surface residual;
(3) electrochemical deoiling: the zinc alloy diecasting after upper step washing is soaked in degreaser solution, to remove the grease on zinc alloy diecasting surface, obtains the zinc alloy diecasting after oil removing;
(4) wash: the zinc alloy diecasting after upper step oil removing is washed, removes the degreaser solution of surface residual;
(5) sulfuric acid activated: the zinc alloy diecasting after upper step washing to be soaked in sulphuric acid soln, to obtain the zinc alloy diecasting activated; The volume fraction of described sulphuric acid soln is 0.5%, and the time of immersion is 10-30s;
(6) wash: the zinc alloy diecasting after upper step activation is washed, removes the sulphuric acid soln of surface residual;
(7) without cyaniding alloy treatment: the solution adopting preparation, containing mantoquita, zinc salt, complexing agent and grain-refining agent in solution, content of copper ion is 2-10g/L, zinc ion concentration is 0-50g/L, complexing agent content is 50-100g/L, grain-refining agent is 0.01-1g/L, and the concentration of OH-free in solution is adjusted to 10-12mol/L; Upper step is washed clean zinc alloy diecasting and is soaked in 3 ~ 8min in this solution, obtain alloy layer; Described grain-refining agent is at least one in glycerine, butynediol, glycerol; Described zinc salt is at least one in zinc nitrate, zinc chloride, zinc sulfate, zinc pyrophosphate, zinc oxide, zinc carbonate, zinc acetate;
(8) wash: the zinc alloy diecasting after upper step alloying is washed, remove surface residual without cyanogen solution;
(9) follow-up plating or electroless plating: the zinc alloy diecasting containing alloy layer clean for upper step washing is carried out follow-up plating or electroless plating process.
Preferably, in step (3), described degreaser solution is made up of tertiary sodium phosphate, sodium carbonate, BH-7 degreaser and water, and wherein the concentration of tertiary sodium phosphate is 28-32g/L, and the concentration of sodium carbonate is the concentration of 28-32g/L, BH-7 degreaser is 10 ~ 20ml/L.
Preferably, in step (7), described mantoquita is at least one in cupric nitrate, cupric chloride, copper sulfate, cupric pyrophosphate, copper hydroxide, ventilation breather, cupric tartrate, Cuprocitrol, Copper Sulfo Salicylic Acid, copper methanesulfonate.
Preferably, in step (7), described complexing agent is tartrate, soluble tartrate, Seignette salt, sodium tartrate, ammonium tartrate, citric acid, Tripotassium Citrate, Trisodium Citrate, ammonium citrate, Sunmorl N 60S, EDETATE SODIUM, sulphosalicylic acid, NTA, diethylene triamine pentamethylene phosphonic, trolamine, quadrol, bicine N-, halfcystine, triethylene tetramine, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid potassium, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid sodium, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid ammonium, ethylene diamine tetra methylene phosphonic acid, ethylene diamine tetra methylene phosphonic acid potassium, ethylene diamine tetra methylene phosphonic acid sodium, at least one in ethylene diamine tetra methylene phosphonic acid ammonium.
Preferably, in step (7), use the concentration of the free OH-at least one regulator solution in KOH, NaOH to 10-12mol/L.
Technical scheme of the present invention has following beneficial effect:
1, without solution used in cyaniding alloy treatment not containing prussiate and nontoxic, nonhazardous gas effusion in immersion process;
2, without in cyaniding alloy treatment, without the need to power supply, without the need to heating, simple to operate.
3, on the basis ensureing the bonding force between coating and matrix, the alternative hydride systems preplating of the present invention, realizes the object that environment-protecting clean is produced.
4, the alloy layer formed is fine and close.
Embodiment
In order to have a clear understanding of technical scheme of the present invention, its detailed structure will be proposed in the following description.Obviously, the concrete execution of the embodiment of the present invention also not enough specific details being limited to those skilled in the art and haveing the knack of.The preferred embodiments of the present invention are described in detail as follows, and except these embodiments described in detail, can also have other embodiments.
A kind of zinc alloy diecasting surface treatment method, comprises the steps:
(1) zinc alloy diecasting blank paraffin removal: be immersed in wax removing agent solution by zinc alloy diecasting blank, removes the wax of zinc alloy diecasting blank surface, obtains the zinc alloy diecasting after paraffin removal; The BH-20 wax removing agent solution of described cerate solution to be concentration be 30 ~ 50ml/L;
(2) wash: the zinc alloy diecasting after paraffin removal is washed, removes the wax removing agent solution of surface residual;
(3) electrochemical deoiling: the zinc alloy diecasting after upper step washing is soaked in degreaser solution, to remove the grease on zinc alloy diecasting surface, obtains the zinc alloy diecasting after oil removing;
(4) wash: the zinc alloy diecasting after upper step oil removing is washed, removes the degreaser solution of surface residual;
(5) sulfuric acid activated: the zinc alloy diecasting after upper step washing to be soaked in sulphuric acid soln, to obtain the zinc alloy diecasting activated; The volume fraction of described sulphuric acid soln is 0.5%, and the time of immersion is 10-30s;
(6) wash: the zinc alloy diecasting after upper step activation is washed, removes the sulphuric acid soln of surface residual;
(7) without cyaniding alloy treatment: the solution adopting preparation, containing mantoquita, zinc salt, complexing agent and grain-refining agent in solution, content of copper ion is 2-10g/L, zinc ion concentration is 0-50g/L, complexing agent content is 50-100g/L, grain-refining agent is 0.01-1g/L, and the concentration of OH-free in solution is adjusted to 10-12mol/L; Upper step is washed clean zinc alloy diecasting and is soaked in 3 ~ 8min in this solution, obtain alloy layer; Described grain-refining agent is at least one in glycerine, butynediol, glycerol; Described zinc salt is at least one in zinc nitrate, zinc chloride, zinc sulfate, zinc pyrophosphate, zinc oxide, zinc carbonate, zinc acetate;
(8) wash: the zinc alloy diecasting after upper step alloying is washed, remove surface residual without cyanogen solution;
(9) follow-up plating or electroless plating: the zinc alloy diecasting containing alloy layer clean for upper step washing is carried out follow-up plating or electroless plating process.
The copper facing of a alkaline electro:
Potassium pyrophosphate (K4P2O7): 275 grams per liters
Cupric pyrophosphate (Cu2P2O74H2O): 72 grams per liters
Ammoniacal liquor: 3 milliliters/liter
BH-540A:3 milliliter/liter
BH-540B:2.8 milliliter/liter
Temperature: 20-40 DEG C
Cathode current density: 1-6 ampere/square decimeter
Alr mode: pneumatic blending;
B acid bright copper plating
Copper sulfate: 180-220 grams per liter
Sulfuric acid (density=1.84 grams per milliliter): 70 grams per liters
Chlorion: 75 mg/litre
BH-530 acid copper plating brightening agent A:0.3 milliliter/liter
BH-530 acid copper plating brightening agent B:0.5 milliliter/liter
BH-530 acid copper plating brightening agent C:5.2 milliliter/liter
Temperature: 20-40 DEG C
Cathode current density: 1-6 ampere/square decimeter
Alr mode: pneumatic blending
C Bright Nickel Electroplating
Single nickel salt: 2700g/L
Nickelous chloride: 50g/L
Boric acid: 45g/L
BH-988 light nickel key light agent: 0.9ml/L
BH-98 light nickel softening agent: 9ml/L
BH-98 light nickel auxiliary: 4ml/L
BH-98 light nickel wetting agent: 1.6ml/L
PH value: 4.0-4.5
Temperature: 55-60 DEG C
Cathode current density: 2-6A/dm2
Alr mode: pneumatic blending
D trivalent chromium chrome plating
BH-88 conducting salt: 300g/L
BH-88 open cylinder agent: 135g/L
BH-88 auxiliary: 10ml/L
BH-88 wetting agent: 2.7ml/L
Temperature: 45-55 DEG C
PH value: 3.0-3.7
Cathode current density: 3-10A/dm2
Time: 2-5min
Alr mode: weak pneumatic blending
Gained workpiece surface light, without numb sand.By workpiece bows to fracture, incision position is blistering not, illustrates that pre-plating layer has good bonding force.
Embodiment 2:
A kind of zinc alloy diecasting surface treatment method, comprises the steps:
(1) zinc alloy diecasting blank paraffin removal: zinc alloy diecasting blank is immersed in 75 DEG C, concentration is 20min in the BH-20 wax removing agent solution of the Guangzhou the second light industry bureau institute of 50ml/L, remove the wax of zinc alloy diecasting blank surface, obtain the zinc alloy diecasting after paraffin removal.
(2) wash: the zinc alloy diecasting in step (1) after paraffin removal, in 35 DEG C of washings three times, remove the wax removing agent solution of surface residual.
(3) electrochemical deoiling: the zinc alloy diecasting cleaned up in step (2), is immersed in 20min in the degreaser solution of 35 DEG C, removes the grease on zinc alloy diecasting surface, obtain the zinc alloy diecasting after oil removing; In degreaser solution, the concentration of tertiary sodium phosphate is 30g/L, and the concentration of sodium carbonate is 30g/L, and the concentration of the BH-7 degreaser of Guangzhou the second light industry bureau institute is 10ml/L.
(4) wash: the zinc alloy diecasting after the oil removing obtained in step (3), in 35 DEG C of washings three times, remove the degreaser solution of surface residual.
(5) 0.5% is sulfuric acid activated: the zinc alloy diecasting cleaned up in step (4), is soak 10s in the sulphuric acid soln of 0.5% in 35 DEG C in volume fraction, obtains the zinc alloy diecasting activated.
(6) wash: the zinc alloy diecasting of the activation obtained in step (5), in 35 DEG C of washings three times, remove the sulphuric acid soln of surface residual.
(7) cyanide-free plating bath: the zinc alloy diecasting cleaned up in step (6) is soaked in cyanide-free plating bath and carries out chemical treatment, in treating processes, per minute travelling workpiece 8 times, soak time 8min; Described without in cyanogen solution, the concentration of free OH-is the concentration of the free OH-in 11mol/L(sodium hydrate regulator solution), copper ion concentration is 2g/L, zinc ion concentration is 0g/L, soluble tartrate na concn is 30g/L, ethylene diamine tetra methylene phosphonic acid sodium 20g/L, butynediol concentration is 0.5g/L.
(8) wash: the zinc alloy diecasting after step (7) interalloy, in 35 DEG C washing three times, remove surface residual without cyanogen solution.
(9) subsequent electroplating process: the zinc alloy diecasting of the cupric zn alloy coating cleaned up in step (8), operation a, b, c with embodiment 1,
D adopts sexavalent chrome chromium plating, and technique is as follows:
Chromic anhydride: 180g/L
BH-decoration chrome plating A:3ml/L
BH-decoration chrome plating B:10ml/L
Temperature: 32-40 DEG C
Cathode current density: 5-20A/dm2
Anode: lead/tin alloy, 93.7%
Gained workpiece surface light, without numb sand, by workpiece bows to fracture, incision position is blistering not, illustrates that pre-plating layer has good bonding force.
Embodiment 3:
A kind of zinc alloy diecasting surface treatment method, comprises the steps:
(1) zinc alloy diecasting blank paraffin removal: zinc alloy diecasting blank is immersed in 85 DEG C, concentration is 8min in the BH-20 wax removing agent solution of 40ml/L Guangzhou the second light industry bureau institute, remove the wax of zinc alloy diecasting blank surface, obtain the zinc alloy diecasting after paraffin removal.
(2) wash: the zinc alloy diecasting in step (1) after paraffin removal, in 30 DEG C of washings three times, remove the wax removing agent solution of surface residual.
(3) electrochemical deoiling: the zinc alloy diecasting cleaned up in step (2), is immersed in 8min in the degreaser solution of 55 DEG C, removes the grease on zinc alloy diecasting surface, obtain the zinc alloy diecasting after oil removing; In degreaser solution, the concentration of tertiary sodium phosphate is 30g/L, and the concentration of sodium carbonate is 30g/L, and the concentration of the BH-7 degreaser of Guangzhou the second light industry bureau institute is 15ml/L.
(4) wash: the zinc alloy diecasting after the oil removing obtained in step (3), in 30 DEG C of washings three times, remove the degreaser solution of surface residual.
(5) 0.5% is sulfuric acid activated: the zinc alloy diecasting cleaned up in step (4), is soak 30s in the sulphuric acid soln of 0.5% in 30 DEG C in volume fraction, obtains the zinc alloy diecasting activated.
(6) wash: the zinc alloy diecasting of the activation obtained in step (5), in 30 DEG C of washings three times, remove the sulphuric acid soln of surface residual.
(7) cyanide-free plating bath: the zinc alloy diecasting cleaned up in step (6) is soaked in cyanide-free plating bath and carries out chemical treatment, in treating processes, per minute travelling workpiece 8 times, soak time 5min; Described without in cyanogen solution, the concentration of free OH-is the concentration of the free OH-in 12mol/L(sodium hydrate regulator solution), copper ion concentration is 10g/L, zinc ion concentration is 25g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid potassium 80g/L, gluconic acid na concn is 20g/L, and propiolic alcohol concentration is 0.01g/L.
(8) wash: obtain the zinc alloy diecasting after copper zinc alloy in step (7), in 30 DEG C washing three times, remove surface residual without cyanogen alloy solution.
(9) subsequent chemistry depositing process is as follows: the zinc alloy diecasting of the cupric zn alloy coating cleaned up in step (8), immerses following solution and carries out chemical nickel plating:
Single nickel salt: 27g/L
Sodium hypophosphite: 30g/L
Sodium acetate: 8g/L
Trisodium Citrate: 7g/L
Succinic acid: 6g/L
Temperature: 80-90 DEG C
Time: 20-30min
Gained workpiece surface uniform and delicate, by workpiece bows to fracture, incision position is blistering not; By workpiece in 150 DEG C of bakings, be then positioned in cold water, have no foaming, illustrate that pre-plating layer has good bonding force.
Technical scheme of the present invention has following beneficial effect:
1, without solution used in cyaniding alloy treatment not containing prussiate and nontoxic, nonhazardous gas effusion in immersion process;
2, without in cyaniding alloy treatment, without the need to power supply, without the need to heating, simple to operate.
3, on the basis ensureing the bonding force between coating and matrix, the alternative hydride systems preplating of the present invention, realizes the object that environment-protecting clean is produced.
4, the alloy layer formed is fine and close.
Finally should be noted that: above embodiment is only in order to illustrate that technical scheme of the present invention is not intended to limit; although with reference to above-described embodiment to invention has been detailed description; those of ordinary skill in the field still can modify to the specific embodiment of the present invention or equivalent replacement; these do not depart from any amendment of spirit and scope of the invention or equivalent replacement, are all applying within the claims awaited the reply.
Claims (5)
1. a zinc alloy diecasting surface treatment method, is characterized in that, the treating method comprises following steps:
(1) zinc alloy diecasting blank paraffin removal: be immersed in wax removing agent solution by zinc alloy diecasting blank, removes the wax of zinc alloy diecasting blank surface, obtains the zinc alloy diecasting after paraffin removal; The BH-20 wax removing agent solution of described cerate solution to be concentration be 30 ~ 50ml/L;
(2) wash: the zinc alloy diecasting after paraffin removal is washed, removes the wax removing agent solution of surface residual;
(3) electrochemical deoiling: the zinc alloy diecasting after upper step washing is soaked in degreaser solution, to remove the grease on zinc alloy diecasting surface, obtains the zinc alloy diecasting after oil removing;
(4) wash: the zinc alloy diecasting after upper step oil removing is washed, removes the degreaser solution of surface residual;
(5) sulfuric acid activated: the zinc alloy diecasting after upper step washing to be soaked in sulphuric acid soln, to obtain the zinc alloy diecasting activated; The volume fraction of described sulphuric acid soln is 0.5%, and the time of immersion is 10-30s;
(6) wash: the zinc alloy diecasting after upper step activation is washed, removes the sulphuric acid soln of surface residual;
(7) without cyaniding alloy treatment: the solution adopting preparation, containing mantoquita, zinc salt, complexing agent and grain-refining agent in solution, content of copper ion is 2-10g/L, zinc ion concentration is 0-50g/L, complexing agent content is 50-100g/L, grain-refining agent is 0.01-1g/L, and the concentration of OH-free in solution is adjusted to 10-12mol/L; Upper step is washed clean zinc alloy diecasting and is soaked in 3 ~ 8min in this solution, obtain alloy layer; Described grain-refining agent is at least one in glycerine, butynediol, glycerol; Described zinc salt is at least one in zinc nitrate, zinc chloride, zinc sulfate, zinc pyrophosphate, zinc oxide, zinc carbonate, zinc acetate;
(8) wash: the zinc alloy diecasting after upper step alloying is washed, remove surface residual without cyanogen solution;
(9) follow-up plating or electroless plating: the zinc alloy diecasting containing alloy layer clean for upper step washing is carried out follow-up plating or electroless plating process.
2. zinc alloy diecasting surface treatment method according to claim 1, it is characterized in that: in step (3), described degreaser solution is made up of tertiary sodium phosphate, sodium carbonate, BH-7 degreaser and water, wherein the concentration of tertiary sodium phosphate is 28-32g/L, the concentration of sodium carbonate is the concentration of 28-32g/L, BH-7 degreaser is 10 ~ 20ml/L.
3. zinc alloy diecasting surface treatment method according to claim 1, it is characterized in that: in step (7), described mantoquita is at least one in cupric nitrate, cupric chloride, copper sulfate, cupric pyrophosphate, copper hydroxide, ventilation breather, cupric tartrate, Cuprocitrol, Copper Sulfo Salicylic Acid, copper methanesulfonate.
4. zinc alloy diecasting surface treatment method according to claim 1, it is characterized in that: in step (7), described complexing agent is tartrate, soluble tartrate, Seignette salt, sodium tartrate, ammonium tartrate, citric acid, Tripotassium Citrate, Trisodium Citrate, ammonium citrate, Sunmorl N 60S, EDETATE SODIUM, sulphosalicylic acid, NTA, diethylene triamine pentamethylene phosphonic, trolamine, quadrol, bicine N-, halfcystine, triethylene tetramine, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid potassium, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid sodium, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid ammonium, ethylene diamine tetra methylene phosphonic acid, ethylene diamine tetra methylene phosphonic acid potassium, ethylene diamine tetra methylene phosphonic acid sodium, at least one in ethylene diamine tetra methylene phosphonic acid ammonium.
5. zinc alloy diecasting surface treatment method according to claim 1, is characterized in that: in step (7), uses the concentration of the free OH-at least one regulator solution in KOH, NaOH to 10-12mol/L.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106048569A (en) * | 2016-06-12 | 2016-10-26 | 含山县朝霞铸造有限公司 | Surface treatment method for aluminum alloy die casting and product thereof |
| CN111424284A (en) * | 2020-05-06 | 2020-07-17 | 苏州清飙科技有限公司 | Degreasing solution for die-casting zinc alloy and preparation method thereof |
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| CN101012569A (en) * | 2006-12-29 | 2007-08-08 | 哈尔滨工业大学 | Method for direct copper non-cyanide plating of zinc alloy casting die |
| 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 |
| CN103757642A (en) * | 2013-12-18 | 2014-04-30 | 广州鸿葳科技股份有限公司 | Zinc alloy die casting surface treatment method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012569A (en) * | 2006-12-29 | 2007-08-08 | 哈尔滨工业大学 | Method for direct copper non-cyanide plating of zinc alloy casting die |
| 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 |
| CN103757642A (en) * | 2013-12-18 | 2014-04-30 | 广州鸿葳科技股份有限公司 | Zinc alloy die casting surface treatment method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106048569A (en) * | 2016-06-12 | 2016-10-26 | 含山县朝霞铸造有限公司 | Surface treatment method for aluminum alloy die casting and product thereof |
| CN111424284A (en) * | 2020-05-06 | 2020-07-17 | 苏州清飙科技有限公司 | Degreasing solution for die-casting zinc alloy and preparation method thereof |
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