CN105525290A - Magnesium alloy material, terminal, communication device, vehicle and preparation method - Google Patents
Magnesium alloy material, terminal, communication device, vehicle and preparation method Download PDFInfo
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- CN105525290A CN105525290A CN201410572970.9A CN201410572970A CN105525290A CN 105525290 A CN105525290 A CN 105525290A CN 201410572970 A CN201410572970 A CN 201410572970A CN 105525290 A CN105525290 A CN 105525290A
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Abstract
The invention is applicable to the field of materials and provides a magnesium alloy material, comprising a magnesium alloy matrix, a zinc layer adhering to a surface of the magnesium alloy matrix and a passivation film adhering to a surface of the zinc layer. The magnesium alloy material provided by the embodiment of the present invention is good in corrosion resistance and low in resistance.
Description
Technical field
The present invention relates to Material Field, particularly relate to magnesium alloy materials, terminal, communication equipment, the vehicles and preparation method.
Background technology
Magnesium alloy is that base adds other elementary composition alloys with magnesium.It has that density is little, specific tenacity is high, Young's modulus is large, shock absorbing is good, the loading capacity that withstands shocks is than advantages such as aluminium alloy are large.Be mainly used in the industrial sectors such as Aeronautics and Astronautics, transport, chemical industry, rocket.
Existing magnesium alloy materials, be generally by carrying out epithelium process or electro-coppering to magnesium alloy substrate, nickel, chromium process obtain, there is salt fog poor performance in this magnesium alloy materials, the problem that resistance is high.
Summary of the invention
The embodiment of the present invention provides a kind of magnesium alloy materials, is intended to the salt fog poor performance solving existing magnesium alloy materials, the problem that resistance is high.
The embodiment of the present invention is achieved in that a kind of magnesium alloy materials, comprising:
Magnesium alloy substrate;
Zinc layers, is attached to described magnesium alloy matrix surface; And
Passive film, is attached to described zinc layers surface.
The embodiment of the present invention also provides another kind of magnesium alloy materials, comprising:
Magnesium alloy substrate;
Nickel dam, is attached to described magnesium alloy matrix surface;
Zinc layers, is attached to described nickel dam surface; And
Passive film, is attached to described zinc layers surface.
The embodiment of the present invention also provides a kind of mobile terminal, includes termination support and/or terminal connector, it is characterized in that, described termination support and/or terminal connector are made up of above-mentioned magnesium alloy materials in whole or in part.
The embodiment of the present invention also provides a kind of communication equipment, comprises equipment support members and/or equipment connection part, it is characterized in that, described equipment support members and/or equipment connection part are made up of above-mentioned magnesium alloy materials in whole or in part.
The embodiment of the present invention also provides a kind of vehicles, comprises vehicles strut member and/or vehicles web member, it is characterized in that, described vehicles strut member and/or vehicles web member are made up of above-mentioned magnesium alloy materials.
The embodiment of the present invention also provides a kind of preparation method of magnesium alloy materials, it is characterized in that, described method comprises the steps:
Heavy zinc or heavy nickel step: magnesium alloy substrate is placed in the solution containing zine ion or nickel ion, form one deck at described magnesium alloy matrix surface and sink zinc layers or heavy nickel dam;
Pre-zinc-plated step: the magnesium alloy substrate through described heavy zinc or heavy nickel step process is placed in pre-galvanizing solution, forms the pre-zinc coating of one deck in described heavy zinc layers or heavy nickel dam electroplating surface;
Zinc-plated step: the magnesium alloy substrate through described pre-zinc-plated step process is placed in galvanizing solution, forms one deck zinc coating at described pre-zinc coating electroplating surface;
Passivation step: the magnesium alloy substrate through described zinc-plated step process is placed in passivating solution, forms one deck passive film at described Several Thiourea Derivatives on Zinc Plate Surface.
The magnesium alloy materials that the embodiment of the present invention provides, its corrosion resistance and good, resistance is low.
Accompanying drawing explanation
Fig. 1 is the tangent plane structural representation of the first magnesium alloy materials that the embodiment of the present invention 1 provides;
Fig. 2 is the tangent plane structural representation of the second magnesium alloy materials that the embodiment of the present invention 1 provides;
Fig. 3 is the tangent plane structural representation of the third magnesium alloy materials that the embodiment of the present invention 1 provides;
Fig. 4 is the tangent plane structural representation of the 4th kind of magnesium alloy materials that the embodiment of the present invention 1 provides;
Fig. 5 is preparation method's schema of the magnesium alloy materials that the embodiment of the present invention provides.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The magnesium alloy materials that the embodiment of the present invention provides is attached with zinc layers and passive film on magnesium alloy substrate, and make magnesium alloy materials corrosion resistance and good, resistance is low.
Described magnesium alloy substrate in the embodiment of the present invention is the alloy material comprising magnesium, in embodiments of the present invention, the salt fog performance of magnesium alloy materials adopts the testing method in GB/T10125-2012/ISO9227:2006 " artificial atmosphere corrosion test salt-fog test " to test, observe the maximum time that magnesium alloy substrate does not occur to corrode, this cycle observing time be 2,6,24,48,96,144,168,240,480 (h); Conductivity adopts the resistance of ZY9987 type digital microohm meter test sample, the probe diameter of probe is 2mm (millimeter), be applied to the power of probe is 500N (newton), per sample (p.s.) product are got 2 points and are measured, then the resistance of resistance mean value as test agent of 2 points is got, in embodiments of the present invention, before carrying out salt fog performance test and after test, respectively the resistive performance of sample is tested; Bonding force performance adopts the testing method in ISO2409-2007 (E) " paint and varnish-cross cut test " to test.
Embodiment 1:
With reference to figure 1 and Fig. 2, the tangent plane structural representation of the first magnesium alloy materials provided for the embodiment of the present invention 1 and the tangent plane structural representation of the second magnesium alloy materials, for ease of describing, part related to the present invention is only shown, details are as follows.
Magnesium alloy materials comprises magnesium alloy substrate 1, is attached to the zinc layers 2 of magnesium alloy substrate 1, and is attached to the passive film 3 of zinc layers 2.
In embodiments of the present invention, the thickness of zinc layers 2 is 1.9-12.8 μm, preferably 7.5 μm, and density is 0.71 ~ 0.78 ㎎ ㎝
-2μm
-1, preferably 0.71 ㎎ ㎝
-2μm
-1.
In embodiments of the present invention, the thickness of passive film 3 is 0.2-0.6 μm, preferably 0.4 μm.
As another embodiment of the present invention, with reference to figure 3 and Fig. 4, the tangent plane structural representation of the third magnesium alloy materials provided for the embodiment of the present invention 1 and the tangent plane structural representation of the 4th kind of magnesium alloy materials, for ease of describing, part related to the present invention is only shown, details are as follows.
Magnesium alloy materials comprises magnesium alloy substrate 1, is attached to the nickel dam 4 of magnesium alloy substrate 1, is attached to the zinc layers 2 of heavy nickel dam 4 and is attached to the passive film 3 of zinc layers 2.
In embodiments of the present invention, the thickness of nickel dam 4 is 1 ~ 5 μm, preferably 3 μm, and density is 0.89 ~ 0.98 ㎎ ㎝
-2μm
-1, preferably 0.89 ㎎ ㎝
-2μm
-1.
In embodiments of the present invention, the thickness of zinc layers 2 is 1.4-7.8 μm, preferably 5 μm, and density is 0.71 ~ 0.78 ㎎ ㎝
-2μm
-1, preferably 0.71 ㎎ ㎝
-2μm
-1.
In embodiments of the present invention, the thickness of passive film 3 is 0.2-0.6 μm, preferably 0.4 μm.
Magnesium alloy materials in above-mentioned two kinds of embodiments, salt fog performance can reach 96h, resistance before salt fog performance test is at below 0.8m Ω, resistance after salt fog performance test is at below 1.0m Ω, there is not the phenomenon that coating comes off in magnesium alloy substrate 1 surface after bonding force performance test, its corrosion resistance and good, resistance is little, and bonding force is strong.
Embodiment 2:
A kind of mobile terminal, comprise termination support and/or terminal connector, all or part of employing magnesium alloy materials of termination support and/or terminal connector is made.
In embodiments of the present invention, described termination support comprises shell or the support of mobile terminal, and described shell is mobile terminal outermost layer structural part, and described support is passive framework in mobile terminal.
In embodiments of the present invention, described terminal connector comprises the screw, screw etc. in mobile terminal.
As one embodiment of the invention, with reference to Fig. 1 and 2, described magnesium alloy materials comprises magnesium alloy substrate 1, is attached to the zinc layers 2 of magnesium alloy substrate 1, and is attached to the passive film 3 of zinc layers 2.
In embodiments of the present invention, the thickness of described zinc layers 2 is 1.9-12.8 μm, preferably 7.5 μm, and density is 0.71 ~ 0.78 ㎎ ㎝
-2μm
-1, preferably 0.71 ㎎ ㎝
-2μm
-1.
In embodiments of the present invention, the thickness of described passive film 3 is 0.2-0.6 μm, preferably 0.4 μm.
As another embodiment of the present invention, with reference to figure 3 and 4, described magnesium alloy materials comprises magnesium alloy substrate 1, the nickel dam 4 being attached to magnesium alloy substrate 1, the zinc layers 2 being attached to nickel dam 4 and be attached to the passive film 3 of zinc layers 2.
In embodiments of the present invention, the thickness of described nickel dam 4 is 1 ~ 5 μm, preferably 3 μm, and density is 0.89 ~ 0.98 ㎎ ㎝
-2μm
-1, preferably 0.89 ㎎ ㎝
-2μm
-1.
In embodiments of the present invention, the thickness of described zinc layers 2 is 1.4-7.8 μm, preferably 5 μm, and density is 0.71 ~ 0.78 ㎎ ㎝
-2μm
-1, preferably 0.71 ㎎ ㎝
-2μm
-1.
In embodiments of the present invention, the thickness of described passive film 3 is 0.2-0.6 μm, preferably 0.4 μm.
In embodiments of the present invention, described mobile terminal includes but not limited to mobile telephone, Personal Computer or personal digital assistant (PDA).
In embodiments of the present invention, the magnesium alloy materials that the termination support of described mobile terminal and/or terminal connector adopt, has light, salt fog good, the good performance such as resistance is little of quality, makes mobile terminal lighter, corrosion-resistant and the loss of signal is little.
Embodiment 3:
A kind of communication equipment, comprise equipment support members and/or equipment connection part, all or part of employing magnesium alloy materials of equipment support members and/or equipment connection part is made.
In embodiments of the present invention, described equipment support members comprises the skeleton construction of the shell of communication equipment, support or internal component, described shell is communication equipment or outermost layer structural part, described support is passive framework in communication equipment, and the skeleton construction of described internal component is as the shell of wave filter and support etc.
In embodiments of the present invention, described equipment connection part comprises the screw, screw etc. in communication equipment.
As one embodiment of the invention, with reference to Fig. 1 and 2, described magnesium alloy materials comprises magnesium alloy substrate 1, is attached to the zinc layers 2 of magnesium alloy substrate 1, and is attached to the passive film 3 of zinc layers 2.
In embodiments of the present invention, the thickness of described zinc layers 2 is 1.9-12.8 μm, preferably 7.5 μm, and density is 0.71 ~ 0.78 ㎎ ㎝
-2μm
-1, preferably 0.71 ㎎ ㎝
-2μm
-1.
In embodiments of the present invention, the thickness of described passive film 3 is 0.2-0.6 μm, preferably 0.4 μm.
As another embodiment of the present invention, with reference to figure 3 and 4, described magnesium alloy materials comprises magnesium alloy substrate 1, the nickel dam 4 being attached to magnesium alloy substrate 1, the zinc layers 2 being attached to nickel dam 4 and be attached to the passive film 3 of zinc layers 2.
In embodiments of the present invention, the thickness of described nickel dam 4 is 1 ~ 5 μm, preferably 3 μm, and density is 0.89 ~ 0.98 ㎎ ㎝
-2μm
-1, preferably 0.89 ㎎ ㎝
-2μm
-1.
In embodiments of the present invention, the thickness of described zinc layers 2 is 1.4-7.8 μm, preferably 5 μm, and density is 0.71 ~ 0.78 ㎎ ㎝
-2μm
-1, preferably 0.71 ㎎ ㎝
-2μm
-1.
In embodiments of the present invention, the thickness of described passive film 3 is 0.2-0.6 μm, preferably 0.4 μm.
In embodiments of the present invention, described mobile terminal includes but not limited to base station, modulator-demodulator unit or communication projector.
In embodiments of the present invention, the magnesium alloy materials that the equipment support members of described communication equipment and/or equipment connection part adopt, has light, salt fog good, the good performance such as resistance is little of quality, makes communication equipment lighter, corrosion-resistant and the loss of signal is little.
Embodiment 4
A kind of vehicles, comprise vehicles strut member and/or vehicles web member, all or part of employing magnesium alloy materials of vehicles strut member and/or vehicles web member is made.
In embodiments of the present invention, vehicles strut member comprises the skeleton construction of the shell of the vehicles, support or internal component, described shell is communication equipment or outermost layer structural part, described support is passive framework in communication equipment, and the skeleton construction of described internal component is as engine case, motor housing etc.
In embodiments of the present invention, described vehicles web member comprises the screw, screw etc. in the vehicles.
As one embodiment of the invention, with reference to Fig. 1 and 2, described magnesium alloy materials comprises magnesium alloy substrate 1, is attached to the zinc layers 2 of magnesium alloy substrate 1, and is attached to the passive film 3 of zinc layers 2.
In embodiments of the present invention, the thickness of described zinc layers 2 is 1.9-12.8 μm, preferably 7.5 μm, and density is 0.71 ~ 0.78 ㎎ ㎝
-2μm
-1, preferably 0.71 ㎎ ㎝
-2μm
-1.
In embodiments of the present invention, the thickness of described passive film 3 is 0.2-0.6 μm, preferably 0.4 μm.
As another embodiment of the present invention, with reference to figure 3 and 4, described magnesium alloy materials comprises magnesium alloy substrate 1, the nickel dam 4 being attached to magnesium alloy substrate 1, the zinc layers 2 being attached to nickel dam 4 and be attached to the passive film 3 of zinc layers 2.
In embodiments of the present invention, the thickness of described nickel dam 4 is 1 ~ 5 μm, preferably 3 μm, and density is 0.89 ~ 0.98 ㎎ ㎝
-2μm
-1, preferably 0.89 ㎎ ㎝
-2μm
-1.
In embodiments of the present invention, the thickness of described zinc layers 2 is 1.4-7.8 μm, preferably 5 μm, and density is 0.71 ~ 0.78 ㎎ ㎝
-2μm
-1, preferably 0.71 ㎎ ㎝
-2μm
-1.
In embodiments of the present invention, the thickness of described passive film 3 is 0.2-0.6 μm, preferably 0.4 μm.
In embodiments of the present invention, the described vehicles include but not limited to automobile and track vehicle, as subway or train.
In embodiments of the present invention, the magnesium alloy materials that the vehicles strut member of the described vehicles and/or vehicles web member adopt, has light, the salt fog good performance of quality, makes the vehicles lighter, reduce in the process of moving to use and consume, corrosion-resistant in use procedure.
Fig. 5 shows preparation method's realization flow of the magnesium alloy materials that the embodiment of the present invention provides, and details are as follows:
Pre-treatment step: for removing the spot on magnesium alloy substrate 1 surface, smooth magnesium alloy substrate 1 surface.
In embodiments of the present invention, described spot is included in the greasy dirt attached in the course of processing, and the oxide compound formed in the course of processing and burr etc., pretreated step is carried out to magnesium alloy and adopts the common treatment process of prior art, generally comprise degreasing, alkaline etching, edging and activation.Certainly, in other embodiments of the present invention, pre-treatment step can also comprise other steps such as place to go magnesium alloy substrate 1 surface blot, smooth magnesium alloy substrate 1 surface.
Heavy zinc or heavy nickel step: magnesium alloy substrate 1 is placed in the solution containing zine ion or nickel ion, form one deck on described magnesium alloy substrate 1 surface and sink zinc layers or heavy nickel dam, this heavy zinc layers or heavy nickel dam can strengthen the bonding force between magnesium alloy matrix surface coating and magnesium alloy substrate 1.
As one embodiment of the present of invention, be respectively containing material each in the solution of zine ion and mass percent thereof: zinc oxide 4 ~ 6%, potassium pyrophosphate 20 ~ 28%, sodium phosphate 5 ~ 9%, other are water, and adopt the pH value of ammoniacal liquor regulator solution, pH controls 6.5 ~ 11.5, preferably, control 7 ~ 9.
Implement as of the present invention another, be respectively containing material each in the solution of nickel ion and concentration thereof: citric acid nickel 10 ~ 40g/L, SODIUM PHOSPHATE, MONOBASIC 10 ~ 40g/L, trisodium phosphate 20 ~ 80g/L, Neutral ammonium fluoride 10 ~ 40g/L, and regulate pH to 9 ~ 10.
In an embodiment of the present invention, the temperature of the solution containing zine ion or nickel ion controls at 60 ~ 90 DEG C, preferably, controls at 80 DEG C; Heavy zinc or heavy nickel time controling, at 2 ~ 10min, preferably, control at 5 ~ 10min.
Pre-zinc-plated step: the magnesium alloy substrate 1 through described heavy zinc or heavy nickel step process is placed in pre-galvanizing solution, the pre-zinc coating of one deck is formed in described heavy zinc layers or heavy nickel dam surface, described pre-zinc coating, being isolated from the outside by magnesium alloy substrate 1, prevents galvanizing solution and magnesium alloy substrate 1 in follow-up zinc-plated step from chemical reaction occurring.
In embodiments of the present invention, pre-galvanizing solution is by dissolved oxygen zinc in sodium hydroxide/potassium hydroxide solution, then add preplating complexing agent to obtain, wherein the concentration of sodium hydroxide/potassium hydroxide is 10 ~ 100g/L, oxidation zinc concentration is 5 ~ 14g/L, the concentration of preplating complexing agent is 5 ~ 100g/L, the concentration of salt of wormwood is 0-30g/L, adopts sodium hydroxide/potassium hydroxide to regulate pH to 7.5 ~ 8.5.
As one embodiment of the present of invention, preplating complexing agent be HEDP (hydroxy ethylene diphosphonic acid) aqueous solution, HEDP and carbonate mixed aqueous solution or containing CN ~ the aqueous solution, as sodium cyanide solution, for forming complex compound with the zine ion in pre-galvanizing solution, prevent the magnesium simple substance in magnesium alloy substrate 1 and the zine ion generation replacement(metathesis)reaction in pre-metallization solution and solution in pre-galvanizing solution.
In embodiments of the present invention, in step zinc-plated in advance, using magnesium alloy substrate 1 as negative electrode, zine plate/iron plate is as anode, and the electric current being applied to magnesium alloy substrate 1 is 1 ~ 4A/dm
2, conduction time is 3 ~ 30min.
Zinc-plated step: the magnesium alloy substrate 1 through described pre-zinc-plated step process is placed in galvanizing solution, forms one deck zinc coating at described pre-Several Thiourea Derivatives on Zinc Plate Surface.
In embodiments of the present invention, galvanizing solution is obtained by dissolved oxygen zinc in sodium hydroxide/potassium hydroxide solution, and wherein the concentration of sodium hydroxide/potassium hydroxide is 100 ~ 200g/L, and oxidation zinc concentration is 7 ~ 60g/L.
In embodiments of the present invention, in zinc-plated step, using magnesium alloy substrate 1 as negative electrode, zine plate/iron plate is as anode, and the electric current being applied to magnesium alloy substrate 1 is 0.5 ~ 6A/dm
2, conduction time is 5 ~ 60min.
As a preferred embodiment of the invention, galvanizing solution also comprises the zinc-plated complexing agent of 4 ~ 6ml/L, for ensureing the uniformity coefficient of coating and upper plating speed.
In embodiments of the present invention, zinc-plated complexing agent is formed by nitride and epoxy chloropropane condensation, as DE complexing agent (being formed by epoxy chloropropane and dimethylamine condensation), DPE ~ 3 complexing agent (being formed by dimethylaminopropylamine, quadrol and epoxy chloropropane condensation) etc.As another preferred embodiment of the present invention, galvanizing solution also comprises the key light agent of 2 ~ 15ml/L, for increasing the glossiness of coating.
In embodiments of the present invention, key light agent is weight percentage the thiocarbamide of concentration 0.1 ~ 1%.
As another preferred embodiment of the present invention, galvanizing solution also comprises 2 ~ 15ml/L additive, for strengthening plated layer compact degree, makes magnesium alloy substrate 1 antirust function after electroplating stronger, and more attractive in appearance.
As one embodiment of the present of invention, additive is weight percentage 3-sulfydryl-1,2, the 4-triazole of concentration 1 ~ 2.5%.
Passivation step: the magnesium alloy substrate 1 through described zinc-plated process is placed in passivating solution, forms one deck passive film 3 (trivalent chromium acid layer) at described Several Thiourea Derivatives on Zinc Plate Surface, to increase the corrosion resistance nature of the coating that preceding step is formed.
In embodiments of the present invention, passivating solution can be the aqueous solution comprising chromium nitrate, SODIUMNITRATE and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, and its total concn is 20 ~ 300g/L.
In embodiments of the present invention, the time controling of passivation is at 8 ~ 50s.
As one embodiment of the invention, when select in heavy zinc or heavy nickel step for heavy zinc step time, the zinc coating that the heavy zinc layers that this heavy zinc step is formed on magnesium alloy substrate 1 surface, pre-zinc-plated step are formed at pre-Several Thiourea Derivatives on Zinc Plate Surface in the pre-zinc coating and zinc-plated step of this heavy zinc layers electroplating surface formation merges mutually, the zinc layers 2 of common composition magnesium alloy materials as illustrated in fig. 1 and 2, the passive film formed at Several Thiourea Derivatives on Zinc Plate Surface in passivation step is the passive film 3 of magnesium alloy materials as illustrated in fig. 1 and 2.
As another embodiment of the present invention, when select in heavy zinc or heavy nickel step for heavy nickel step time, this heavy nickel step is the nickel dam 4 of magnesium alloy materials as shown in Figures 3 and 4 at the heavy nickel dam that magnesium alloy substrate 1 surface is formed, the zinc coating that pre-zinc-plated step is formed at pre-Several Thiourea Derivatives on Zinc Plate Surface in the pre-zinc coating and zinc-plated step of this heavy zinc layers electroplating surface formation merges mutually, the zinc layers 2 of common composition magnesium alloy materials as shown in Figures 3 and 4, the passive film formed at Several Thiourea Derivatives on Zinc Plate Surface in passivation step is the passive film 3 of magnesium alloy materials as shown in Figures 3 and 4.
Process and the effect of the surface treatment method of Mg alloy of the embodiment of the present invention is further illustrated below by embodiment.
Embodiment 5:
The preparation of zine ion solution: take 4g zinc oxide, 20g potassium pyrophosphate and 5g sodium phosphate respectively, is dissolved in water as the aqueous solution of 100g, adopts
ammoniawater regulates pH to 6.5, obtained zine ion solution.
The preparation of pre-galvanizing solution: the zinc oxide taking 10g sodium hydroxide, 5g, the HEDP that 5g Guangzhou Chuan Qi Chemical Co., Ltd. produces; The sodium hydroxide taken is divided into two parts, a mixes with zinc oxide, furnishing pasty state, another part mixes with HEDP; By above-mentioned two kinds of mixtures mixing, and adopt sodium hydroxide to regulate PH to be 7.5, add the mixing of 30g salt of wormwood afterwards, be diluted with water to 1L, obtained pre-galvanizing solution.
The preparation of galvanizing solution: the zinc oxide taking 100g sodium hydroxide, 7g, both mixing, furnishing pasty state; The zinc-plated complexing agent (Atotech (China) Chemical Co., Ltd. P3000 series open cylinder agent) of 4ml and the 3-sulfydryl-1 of 15g is added in said mixture, 2,4-triazole (weight percent is 2.5%), is diluted with water to 1L, obtained galvanizing solution.
The zine ion solution configured is housed in plating tank; Will be heated to the zine ion solution 10min of 60 DEG C by being placed in through pretreated magnesium alloy substrate 1, taking out, wash.
The pre-galvanizing solution prepared is housed in plating tank; Using the magnesium alloy substrate 1 through above-mentioned heavy zinc process as negative electrode, zine plate/iron plate is as anode, and to both energisings, electrical current is 1A/dm
2, take out after energising 30min, wash.
The galvanizing solution prepared is housed in plating tank; Using the magnesium alloy substrate 1 through pre-zinc-plated process as negative electrode, zine plate/iron plate is as anode, and to both energisings, electrical current is 6A/dm
2, take out after energising 5min, wash.
Magnesium alloy substrate 1 after zinc-plated process is placed in passivating solution (high-performance that Atotech (China) Chemical Co., Ltd. produces blue zinc passivating solution HC2), passivation 50s, period constantly stirs, then take out, wash, dry, namely obtain surface treated magnesium alloy materials.
To being carried out salt fog performance test, resistive performance test and bonding force performance test by the magnesium alloy substrate 1 after aforesaid method process.Table 1 shows test result.
Embodiment 6:
The preparation of nickel ion solution: take 10g citric acid nickel, 10g SODIUM PHOSPHATE, MONOBASIC, 20g trisodium phosphate and 10g Neutral ammonium fluoride respectively, be dissolved in water to 1L, adopts ammoniacal liquor to regulate pH to 9, obtained nickel ion solution.
The preparation of pre-galvanizing solution: the zinc oxide taking 40g sodium hydroxide, 8g, the HEDP that 20g Guangzhou Chuan Qi Chemical Co., Ltd. produces; The sodium hydroxide taken is divided into two parts, a mixes with zinc oxide, furnishing pasty state, another part mixes with HEDP; By above-mentioned two kinds of mixtures mixing, and adopt sodium hydroxide to regulate pH to be 8, add the mixing of 25g salt of wormwood afterwards, be diluted with water to 1L, obtained pre-galvanizing solution.
The preparation of galvanizing solution: the zinc oxide taking 120g sodium hydroxide, 15g, both mixing, furnishing pasty state; The zinc-plated complexing agent (Atotech (China) Chemical Co., Ltd. P3000 series open cylinder agent) of 5ml, the thiocarbamide (weight percent is 1%) of 2g and the 3-sulfydryl-1 of 12g is added in said mixture, 2,4-triazole (weight percent is 2.0%), be diluted with water to 1L, obtained galvanizing solution.
The nickel ion solution configured is housed in plating tank; Will be heated to the nickel ion solution 9min of 65 DEG C by being placed in through pretreated magnesium alloy substrate 1, taking out, wash.
The pre-galvanizing solution prepared is housed in plating tank; Using the magnesium alloy substrate 1 through above-mentioned heavy nickel process as negative electrode, zine plate/iron plate is as anode, and to both energisings, electrical current is 1.5A/dm
2, take out after energising 25min, wash.
The galvanizing solution prepared is housed in plating tank; Using the magnesium alloy substrate 1 through pre-zinc-plated process as negative electrode, zine plate/iron plate is as anode, and to both energisings, electrical current is 5.5A/dm
2, take out after energising 15min, wash.
Magnesium alloy substrate 1 after zinc-plated process is placed in passivating solution (high-performance that Atotech (China) Chemical Co., Ltd. produces blue zinc passivating solution HC2), passivation 45s, period constantly stirs, then take out, wash, dry, namely obtain surface treated magnesium alloy materials.
To being carried out salt fog performance test, resistive performance test and bonding force performance test by the magnesium alloy substrate 1 after aforesaid method process.Table 1 shows test result.
Embodiment 7:
The preparation of zine ion solution: take 4.5g zinc oxide, 22g potassium pyrophosphate and 6g sodium phosphate respectively, is dissolved in water as the aqueous solution of 100g, adopts ammoniacal liquor to regulate pH to 11, obtained zine ion solution.
The preparation of pre-galvanizing solution: the zinc oxide taking 70g sodium hydroxide, 12g, the HEDP that 50g Guangzhou Chuan Qi Chemical Co., Ltd. produces; The sodium hydroxide taken is divided into two parts, a mixes with zinc oxide, furnishing pasty state, another part mixes with HEDP; By above-mentioned two kinds of mixtures mixing, and adopt sodium hydroxide to regulate pH to be 8.5, add the mixing of 20g salt of wormwood afterwards, be diluted with water to 1L, obtained pre-galvanizing solution.
The preparation of galvanizing solution: the zinc oxide taking 140g sodium hydroxide, 20g, both mixing, furnishing pasty state; The zinc-plated complexing agent (Atotech (China) Chemical Co., Ltd. P3000 series open cylinder agent) of 6ml, the thiocarbamide (weight percent is 0.8%) of 5g and the 3-sulfydryl-1 of 10g is added in said mixture, 2,4-triazole (weight percent is 1.5%), be diluted with water to 1L, obtained galvanizing solution.
The zine ion solution configured is housed in plating tank; Will be heated to the zine ion solution 8min of 70 DEG C by being placed in through pretreated magnesium alloy substrate 1, taking out, wash.
The pre-galvanizing solution prepared is housed in plating tank; Using the magnesium alloy substrate 1 through above-mentioned heavy zinc process as negative electrode, zine plate/iron plate is as anode, and to both energisings, electrical current is 2A/dm
2, take out after energising 20min, wash.
The galvanizing solution prepared is housed in plating tank; Using the magnesium alloy substrate 1 through pre-zinc-plated process as negative electrode, zine plate/iron plate is as anode, and to both energisings, electrical current is 5A/dm
2, take out after energising 25min, wash.
Magnesium alloy substrate 1 after zinc-plated process is placed in passivating solution (high-performance that Atotech (China) Chemical Co., Ltd. produces blue zinc passivating solution HC2), passivation 40s, period constantly stirs, then take out, wash, dry, namely obtain surface treated magnesium alloy materials.
To being carried out salt fog performance test, resistive performance test and bonding force performance test by the magnesium alloy substrate 1 after aforesaid method process.Table 1 shows test result.
Embodiment 8:
The preparation of nickel ion solution: take 20g citric acid nickel, 20g SODIUM PHOSPHATE, MONOBASIC, 40g trisodium phosphate and 20g Neutral ammonium fluoride respectively, be dissolved in water to 1L, adopts ammoniacal liquor to regulate pH to 9.3, obtained nickel ion solution.
The preparation of pre-galvanizing solution: the zinc oxide taking 100g sodium hydroxide, 14g, 100g sodium cyanide; The sodium hydroxide taken is mixed with zinc oxide, furnishing pasty state, add take sodium cyanide mixing; By said mixture, and adopt sodium hydroxide to regulate pH to be 8.2, add the mixing of 15g salt of wormwood afterwards, be diluted with water to 1L, obtained pre-galvanizing solution.
The preparation of galvanizing solution: the zinc oxide taking 150g sodium hydroxide, 25g, both mixing, furnishing pasty state; The zinc-plated complexing agent (Atotech (China) Chemical Co., Ltd. P3000 series open cylinder agent) of 4ml, the thiocarbamide (weight percent is 0.1%) of 8g and the 3-sulfydryl-1 of 8g is added in said mixture, 2,4-triazole (weight percent is 1%), be diluted with water to 1L, obtained galvanizing solution.
The nickel ion solution configured is housed in plating tank; Will be heated to the nickel ion solution 6min of 75 DEG C by being placed in through pretreated magnesium alloy substrate 1, taking out, wash.
The pre-galvanizing solution prepared is housed in plating tank; Using the magnesium alloy substrate 1 through above-mentioned heavy nickel process as negative electrode, zine plate/iron plate is as anode, and to both energisings, electrical current is 2.5A/dm
2, take out after energising 18min, wash.
The galvanizing solution prepared is housed in plating tank; Using the magnesium alloy substrate 1 through pre-zinc-plated process as negative electrode, zine plate/iron plate is as anode, and to both energisings, electrical current is 4.5A/dm
2, take out after energising 35min, wash.
Magnesium alloy substrate 1 after zinc-plated process is placed in passivating solution (high-performance that Atotech (China) Chemical Co., Ltd. produces blue zinc passivating solution HC2), passivation 35s, period constantly stirs, then take out, wash, dry, namely obtain surface treated magnesium alloy materials.
To being carried out salt fog performance test, resistive performance test and bonding force performance test by the magnesium alloy substrate 1 after aforesaid method process.Table 1 shows test result.
Embodiment 9:
The preparation of zine ion solution: take 5g zinc oxide, 25g potassium pyrophosphate and 7g sodium phosphate respectively, is dissolved in water as the aqueous solution of 100g, adopts ammoniacal liquor to regulate pH to 7.5, obtained zine ion solution.
The preparation of pre-galvanizing solution: the zinc oxide taking 10g potassium hydroxide, 5g, the HEDP that 10g Guangzhou Chuan Qi Chemical Co., Ltd. produces; The potassium hydroxide taken is divided into two parts, a mixes with zinc oxide, furnishing pasty state, another part mixes with HEDP; By above-mentioned two kinds of mixtures mixing, and adopt potassium hydroxide to regulate pH to be 8, add the mixing of 12g salt of wormwood afterwards, be diluted with water to 1L, obtained pre-galvanizing solution.
The preparation of galvanizing solution: the zinc oxide taking 160g potassium hydroxide, 35g, both mixing, furnishing pasty state; The zinc-plated complexing agent (Atotech (China) Chemical Co., Ltd. P3000 series open cylinder agent) of 5ml, the thiocarbamide (weight percent is 0.3%) of 10g and the 3-sulfydryl-1 of 5g is added in said mixture, 2,4-triazole (weight percent is 2%), be diluted with water to 1L, obtained galvanizing solution.
The zine ion solution configured is housed in plating tank; Will be heated to the zine ion solution 5min of 78 DEG C by being placed in through pretreated magnesium alloy substrate 1, taking out, wash.
The pre-galvanizing solution prepared is housed in plating tank; Using the magnesium alloy substrate 1 through above-mentioned heavy zinc process as negative electrode, zine plate/iron plate is as anode, and to both energisings, electrical current is 2.8A/dm
2, take out after energising 15min, wash.
The galvanizing solution prepared is housed in plating tank; Using the magnesium alloy substrate 1 through pre-zinc-plated process as negative electrode, zine plate/iron plate is as anode, and to both energisings, electrical current is 4A/dm
2, take out after energising 40min, wash.
Magnesium alloy substrate 1 after zinc-plated process is placed in passivating solution (high-performance that Atotech (China) Chemical Co., Ltd. produces blue zinc passivating solution HC2), passivation 30s, period constantly stirs, then take out, wash, dry, namely obtain surface treated magnesium alloy materials.
To being carried out salt fog performance test, resistive performance test and bonding force performance test by the magnesium alloy substrate 1 after aforesaid method process.Table 1 shows test result.
Embodiment 10:
The preparation of nickel ion solution: take 30g citric acid nickel, 30g SODIUM PHOSPHATE, MONOBASIC, 60g trisodium phosphate and 30g Neutral ammonium fluoride respectively, be dissolved in water to 1L, adopts ammoniacal liquor to regulate pH to 9.6, obtained nickel ion solution.
The preparation of pre-galvanizing solution: the zinc oxide taking 40g potassium hydroxide, 8g, 50g sodium cyanide; The potassium hydroxide taken is mixed with zinc oxide, furnishing pasty state, add the sodium cyanide taken; Adopted by said mixture potassium hydroxide to regulate pH to be 7.6, add the mixing of 8g salt of wormwood afterwards, be diluted with water to 1L, obtained pre-galvanizing solution.
The preparation of galvanizing solution: the zinc oxide taking 170g potassium hydroxide, 45g, both mixing, furnishing pasty state; In said mixture, add the zinc-plated complexing agent (Atotech (China) Chemical Co., Ltd. P3000 series open cylinder agent) of 6ml, be diluted with water to 1L, obtained galvanizing solution.
The nickel ion solution configured is housed in plating tank; Will be heated to the nickel ion solution 4min of 80 DEG C by being placed in through pretreated magnesium alloy base 1 body, taking out, wash.
The pre-galvanizing solution prepared is housed in plating tank; Using the magnesium alloy substrate 1 through above-mentioned heavy nickel process as negative electrode, zine plate/iron plate is as anode, and to both energisings, electrical current is 3A/dm
2, take out after energising 10min, wash.
The galvanizing solution prepared is housed in plating tank; Using the magnesium alloy substrate 1 through pre-zinc-plated process as negative electrode, zine plate/iron plate is as anode, and to both energisings, electrical current is 3A/dm
2, take out after energising 45min, wash.
Magnesium alloy substrate 1 after zinc-plated process is placed in passivating solution (high-performance that Atotech (China) Chemical Co., Ltd. produces blue zinc passivating solution HC2), passivation 25s, period constantly stirs, then take out, wash, dry, namely obtain surface treated magnesium alloy materials.
To being carried out salt fog performance test, resistive performance test and bonding force performance test by the magnesium alloy substrate 1 after aforesaid method process.Table 1 shows test result.
Embodiment 11:
The preparation of zine ion solution: take 6g zinc oxide, 28g potassium pyrophosphate and 9g sodium phosphate respectively, is dissolved in water as the aqueous solution of 100g, adopts ammoniacal liquor to regulate pH to 9, obtained zine ion solution.
The preparation of pre-galvanizing solution: the zinc oxide taking 70g potassium hydroxide, 12g, the HEDP that 35g Guangzhou Chuan Qi Chemical Co., Ltd. produces; The potassium hydroxide taken is divided into two parts, a mixes with zinc oxide, furnishing pasty state, another part mixes with HEDP; By above-mentioned two kinds of mixtures mixing, and adopt potassium hydroxide to regulate pH to be 7.9, add the mixing of 3g salt of wormwood afterwards, be diluted with water to 1L, obtained pre-galvanizing solution.
The preparation of galvanizing solution: the zinc oxide taking 180g potassium hydroxide, 55g, both mixing, furnishing pasty state; The zinc-plated complexing agent (Atotech (China) Chemical Co., Ltd. P3000 series open cylinder agent) of 5.5ml, the thiocarbamide (weight percent is 0.8%) of 12g and the 3-sulfydryl-1 of 2g is added in said mixture, 2,4-triazole (weight percent is 2.2%), be diluted with water to 1L, obtained galvanizing solution.
The zine ion solution configured is housed in plating tank; Will be heated to the zine ion solution 3min of 85 DEG C by being placed in through pretreated magnesium alloy substrate 1, taking out, wash.
The pre-galvanizing solution prepared is housed in plating tank; Using the magnesium alloy substrate 1 through above-mentioned heavy zinc process as negative electrode, zine plate/iron plate is as anode, and to both energisings, electrical current is 3.5A/dm
2, take out after energising 5min, wash.
The galvanizing solution prepared is housed in plating tank; Using the magnesium alloy substrate 1 through pre-zinc-plated process as negative electrode, zine plate/iron plate is as anode, and to both energisings, electrical current is 2A/dm
2, take out after energising 50min, wash.
Magnesium alloy substrate 1 after zinc-plated process is placed in passivating solution (high-performance that Atotech (China) Chemical Co., Ltd. produces blue zinc passivating solution HC2), passivation 15s, period constantly stirs, then take out, wash, dry, namely obtain surface treated magnesium alloy materials.
To being carried out salt fog performance test, resistive performance test and bonding force performance test by the magnesium alloy substrate 1 after aforesaid method process.Table 1 shows test result.
Embodiment 12:
The preparation of nickel ion solution: take 40g citric acid nickel, 40g SODIUM PHOSPHATE, MONOBASIC, 80g trisodium phosphate and 40g Neutral ammonium fluoride respectively, be dissolved in water to 1L, adopts ammoniacal liquor to regulate pH to 10, obtained nickel ion solution.
The preparation of pre-galvanizing solution: the zinc oxide taking 100g potassium hydroxide, 14g, the HEDP that 100g Guangzhou Chuan Qi Chemical Co., Ltd. produces; The potassium hydroxide taken is divided into two parts, a mixes with zinc oxide, furnishing pasty state, another part mixes with HEDP; By above-mentioned two kinds of mixtures mixing, and adopt potassium hydroxide to regulate pH to be 8.4, be diluted with water to 1L, obtained pre-galvanizing solution.
The preparation of galvanizing solution: the zinc oxide taking 200g potassium hydroxide, 60g, both mixing, furnishing pasty state; The zinc-plated complexing agent (Atotech (China) Chemical Co., Ltd. P3000 series open cylinder agent) of 4.5ml and the thiocarbamide (weight percent is 1.2%) of 15g is added in said mixture, be diluted with water to 1L, obtained galvanizing solution.
The nickel ion solution configured is housed in plating tank; Will be heated to the nickel ion solution 2min of 90 DEG C by being placed in through pretreated magnesium alloy substrate 1, taking out, wash.
The pre-galvanizing solution prepared is housed in plating tank; Using the magnesium alloy substrate 1 through above-mentioned heavy nickel process as negative electrode, zine plate/iron plate is as anode, and to both energisings, electrical current is 4A/dm
2, take out after energising 3min, wash.
The galvanizing solution prepared is housed in plating tank; Using the magnesium alloy substrate 1 through pre-zinc-plated process as negative electrode, zine plate/iron plate is as anode, and to both energisings, electrical current is 0.5A/dm
2, take out after energising 60min, wash.
Magnesium alloy substrate 1 after zinc-plated process is placed in passivating solution (high-performance that Atotech (China) Chemical Co., Ltd. produces blue zinc passivating solution HC2), passivation 8s, period constantly stirs, then take out, wash, dry, namely obtain surface treated magnesium alloy materials.
To being carried out salt fog performance test, resistive performance test and bonding force performance test by the magnesium alloy substrate 1 after aforesaid method process.Table 1 shows test result.
Table 1:
In conjunction with the smog performance of the magnesium alloy materials of each embodiment in upper table, resistive performance and bonding force performance can be found out, its salt fog performance of magnesium alloy substrate 1 after the surface treatment method of Mg alloy process that the embodiment of the present invention provides at least can reach 96h, resistance before salt fog performance test is all at below 0.7m Ω, resistance after salt fog performance test is all at below 0.8m Ω, and after bonding force performance test, magnesium alloy substrate 1 surface is the phenomenon occurring that coating comes off.The surface treatment method of Mg alloy process that the visible embodiment of the present invention provides to obtain magnesium alloy materials salt fog performance good, resistance is little, and binding force of cladding material is strong.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (22)
1. a magnesium alloy materials, is characterized in that, described magnesium alloy materials comprises:
Magnesium alloy substrate;
Zinc layers, is attached to described magnesium alloy matrix surface; And
Passive film, is attached to described zinc layers surface.
2. as right wants the magnesium alloy materials as described in 1, it is characterized in that, the thickness of described zinc layers is 1.9-12.8 μm, and density is 0.71 ~ 0.78mgcm
-2μm
-1.
3. magnesium alloy materials as claimed in claim 1 or 2, it is characterized in that, the thickness of described passive film is 0.2-0.6 μm.
4. a magnesium alloy materials, is characterized in that, described magnesium alloy comprises:
Magnesium alloy substrate;
Nickel dam, is attached to described magnesium alloy matrix surface;
Zinc layers, is attached to described nickel dam surface; And
Passive film, is attached to described zinc layers surface.
5. magnesium alloy materials as claimed in claim 4, it is characterized in that, the thickness of described nickel dam is 1 ~ 5 μm, and density is 0.89 ~ 0.98mgcm
-2μm
-1.
6. the magnesium alloy materials as described in claim 4 or 5, is characterized in that, the thickness of described zinc layers is 1.4-7.8 μm, and density is 0.71 ~ 0.78mgcm
-2μm
-1.
7. magnesium alloy materials as claimed in claim 5, it is characterized in that, the thickness of described passive film is 0.2-0.6 μm.
8. a mobile terminal, includes termination support and/or terminal connector, it is characterized in that, described termination support and/or terminal connector are made up of the magnesium alloy materials as described in claim 1 or 4 in whole or in part.
9. mobile terminal as claimed in claim 8, it is characterized in that, described mobile terminal is mobile telephone, Personal Computer or personal digital assistant.
10. a communication equipment, comprises equipment support members and/or equipment connection part, it is characterized in that, described equipment support members and/or equipment connection part are made up of the magnesium alloy materials as described in claim 1 or 4 in whole or in part.
11. communication equipment as claimed in claim 10, is characterized in that, described communication equipment is base station, modulator-demodulator unit or communication projector.
12. 1 kinds of vehicles, comprise vehicles strut member and/or vehicles web member, it is characterized in that, described vehicles strut member and/or vehicles web member are made up of the magnesium alloy materials as described in claim 1 or 4.
13. vehicles as claimed in claim 12, it is characterized in that, the described vehicles are automobile or track vehicle.
The preparation method of 14. 1 kinds of magnesium alloy materials, is characterized in that, described method comprises the steps:
Heavy zinc or heavy nickel step: magnesium alloy substrate is placed in the solution containing zine ion or nickel ion, form one deck at described magnesium alloy matrix surface and sink zinc layers or heavy nickel dam;
Pre-zinc-plated step: the magnesium alloy substrate through described heavy zinc or heavy nickel step process is placed in pre-galvanizing solution, forms the pre-zinc coating of one deck in described heavy zinc layers or heavy nickel dam electroplating surface;
Zinc-plated step: the magnesium alloy substrate through described pre-zinc-plated step process is placed in galvanizing solution, forms one deck zinc coating at described pre-zinc coating electroplating surface;
Passivation step: the magnesium alloy substrate through described zinc-plated step process is placed in passivating solution, forms one deck passive film at described Several Thiourea Derivatives on Zinc Plate Surface.
15. methods as claimed in claim 14, is characterized in that, in the described solution containing zine ion, each material and mass percent thereof are respectively: zinc oxide 4 ~ 6%, potassium pyrophosphate 20 ~ 28%, sodium phosphate 5 ~ 9%, other are pH value to 6.5 ~ 11.5 of water, regulator solution.
16. methods as claimed in claim 14, is characterized in that, in the described solution containing nickel ion, each material and concentration thereof are respectively: citric acid nickel 10 ~ 40g/L, SODIUM PHOSPHATE, MONOBASIC 10 ~ 40g/L, trisodium phosphate 20 ~ 80g/L, Neutral ammonium fluoride 10 ~ 40g/L, pH value to 9 ~ 10 of regulator solution.
17. methods as claimed in claim 14, is characterized in that, in described heavy zinc or heavy nickel step, the described temperature containing the solution of zine ion or nickel ion controls at 60 ~ 90 DEG C, and heavy zinc or heavy nickel time controling are at 2 ~ 10min.
18. methods as claimed in claim 14, it is characterized in that, in described pre-galvanizing solution, each material and per-cent thereof are respectively: sodium hydroxide/potassium hydroxide 10 ~ 100g/L, zinc oxide 5 ~ 14g/L, preplating complexing agent 5 ~ 100g/L, salt of wormwood 0-30g/L, adjust ph to 7.5 ~ 8.5.
19. methods as claimed in claim 18, is characterized in that, described preplating complexing agent is the mixed aqueous solution of the HEDP aqueous solution, HEDP and carbonate or the aqueous solution containing CN-.
20. methods as claimed in claim 14, is characterized in that, in described pre-zinc-plated step, the electric current being applied to magnesium alloy substrate is 1-4A/dm
2, conduction time is 3 ~ 30min.
21. methods as claimed in claim 14, it is characterized in that, described galvanizing solution comprises following material and concentration: sodium hydroxide/potassium hydroxide 100-200g/L, zinc oxide 7-60g/L.
22. methods as claimed in claim 14, is characterized in that, in described zinc-plated step, the electric current being applied to magnesium alloy substrate is 0.5-6A/dm
2, conduction time is 5 ~ 60 minutes.
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| US10638628B2 (en) | 2017-08-30 | 2020-04-28 | Samsung Electronics Co., Ltd. | Network communication device enclosure made of different materials |
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| JPH0631443B2 (en) * | 1989-03-27 | 1994-04-27 | 三菱電機株式会社 | Method for forming plating film on magnesium alloy |
| US6068938A (en) * | 1997-04-15 | 2000-05-30 | Kabushiki Kaisha Kobe Seiko Sho | Magnesium based alloys article and a method thereof |
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2014
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0631443B2 (en) * | 1989-03-27 | 1994-04-27 | 三菱電機株式会社 | Method for forming plating film on magnesium alloy |
| US6068938A (en) * | 1997-04-15 | 2000-05-30 | Kabushiki Kaisha Kobe Seiko Sho | Magnesium based alloys article and a method thereof |
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|---|
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| US10638628B2 (en) | 2017-08-30 | 2020-04-28 | Samsung Electronics Co., Ltd. | Network communication device enclosure made of different materials |
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Application publication date: 20160427 |