CN103818047A - Surface coating structure of engineering plastic and preparation method thereof - Google Patents
Surface coating structure of engineering plastic and preparation method thereof Download PDFInfo
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- CN103818047A CN103818047A CN201410072411.1A CN201410072411A CN103818047A CN 103818047 A CN103818047 A CN 103818047A CN 201410072411 A CN201410072411 A CN 201410072411A CN 103818047 A CN103818047 A CN 103818047A
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Abstract
The invention relates to engineering plastic surface treatment, and particularly relates to a surface coating structure of engineering plastic and a preparation method thereof. The surface coating structure of the engineering plastic comprises, in sequence, a vacuum coating conductive metal layer, a nickel electroplated coating, a PVD corrosion-resistant alloy layer and a PVD color layer. The method includes a step of subjecting the engineering plastic to hydrocarbon vacuum oil removal and drying, transferring and hanging the engineering plastic into a PVD furnace, and subjecting the conductive metal layer to vacuum plating; a step of transferring and hanging the processed engineering plastic product to an electroplating hanger to perform nickel electroplating, performing Watt's nickel electroplating, then performing semi-bright nickel electroplating, subjecting the engineering plastic product to wiredrawing processing, and subjecting the engineering plastic product after the wiredrawing processing to hydrocarbon vacuum oil removal and drying; or a step of transferring and hanging the processed engineering plastic product to an electroplating hanger to perform nickel electroplating, performing Watt's nickel electroplating first, then performing semi-bright nickel electroplating, then performing bright nickel electroplating, and finally performing microporous nickel electroplating; and a step of plating the processed engineering plastic product with the PVD corrosion-resistant alloy layer and the PVD color layer.
Description
Technical field
The present invention relates to engineering plastic surface processing, particularly a kind of engineering plastic surface coating structure and preparation method thereof.
Background technology
Mainly ABS plastic for the plastics of the industry such as bathroom, household electrical appliances at present, or ABS+30%PC plastics, its current surface metalation adopts electroplating processes method to carry out, its technical process is: chemical paraffin removal oil removing → Cr VI alligatoring → palladium salt absorption → reduction → sedimentation chemistry nickel → electro-coppering → semi-bright nickel → bright nickel → microporous nickel → bright chromium, or finally carry out again PVD vacuum coating.In this production procedure, can produce a large amount of waste water and heavy metal ion, such as hexavalent chromium can produce harm to environment, the mankind.
The harm of electrodeposited chromium: the infringement hexavalent chromium compound of human body skin is had and stimulated and irritated effect skin.At the position of contact chromate, mist of chromic acid, as hand, wrist, forearm, neck etc. are located to occur dermatitis.Cr VI enters skin through otch and abrasion, can cause chrome ulcer (claiming again chrome ulcer) because of corrosiveness.The infringement of Cr VI to respiratory system is mainly nasal septum perforate membrane, sphagitis and pneumonia.Infringement Cr VI to internal organ is invaded through alimentary canal, can cause taste and smell to go down, so that disappear.Dosage h also can corrode internal organ; Cause that functions of intestines and stomach reduces, occur stomachache, even intestines and stomach ulcer, also may cause harmful effect to liver.Trivalent chromium has certain injury to the lung of human body.The chromic toxicity of evidence is chromic 1%.
Chinese invention patent 201110030832.4 is open a kind of at plastic rubber substrate surface implementing semi-dry electric plating method, a kind of surface metalation of realizing plastic material is provided, simplify electroplating technology, significantly reduce wastewater discharge, reduce pollution to environment, and expand electrodepositable plastic rubber substrate scope at plastic rubber substrate surface implementing semi-dry electric plating method.Plastic rubber substrate is carried out to anhydrous cleaning and dedusting; Plastic rubber substrate surface is carried out to activation processing the 1st time; Plastic rubber substrate surface after activation processing is implemented to PVD plating bottom, alloy transition layer and metal conducting layer processing successively; Plastic rubber substrate after treatment is carried out to ultrasonic wave water washing and the 2nd activation processing; Plastic rubber substrate Direct Electroplating acid copper after treatment or immigration nickel bath are implemented to nickel plating; Plastic rubber substrate after treatment is moved into chrome-plating bath to carry out last electrodeposited chromium or turns linked to the deposition of carrying out chromium layer into PVD stove.This patent of invention is through mentioning the deposition that can carry out PVD stove and carry out chromium layer after electronickelling, but from whole patent particularly embodiment part not being given in electronickelling, carry out the example of PVD chromium coating and relevant detailed description.
In existing engineering plastic surface metallization, there is following problem, as can not be got rid of plating Cr VI completely in actual production, and cause it to produce great harm to environmental protection, producers.
Summary of the invention
The object of the invention is to the problems referred to above that exist in existing engineering plastic surface metallization, provide and can stop the harm of electrodeposited chromium to environment completely, solve electroplating wastewater emission problem simultaneously, can reduce electroplating wastewater 70%～80%, and there is no a hexavalent chromium wastewater, easier a kind of engineering plastic surface coating structure of wastewater treatment and preparation method thereof.
Described engineering plastic surface coating structure, starts to be followed successively by vacuum coating (PVD) conductive metal layer, electroless nickel layer, PVD corrosion-resistant alloy layer and PVD color layers from the engineering plastic bed of material; The thickness of described vacuum coating (PVD) conductive metal layer is 0.5～2 μ m, and the thickness of electroless nickel layer is 7～15 μ m, and the thickness of PVD corrosion-resistant alloy layer is 0.5～2 μ m, and the thickness of PVD color layers is 0.1～0.3 μ m; Described corrosion resistant alloy can be at least one in zirconium silicon alloy (zirconium silicon atom composition is zirconium 50-98 silicon 2-50), chrome-silicon alloy (chrome-silicon atomic component is chromium 50-98 silicon 2-50), nichrome (nickel chromium triangle atomic component is nickel 50-95 chromium 5-50), titanium silicon (titanium silicon atom composition is titanium 50-98 silicon 2-50) etc.
The preparation method of described engineering plastic surface coating structure, comprises the following steps:
1) engineering plastics vacuum coating PVD pre-metallization: first engineering plastics are carried out to hydrocarbon vacuum oil removing and oven dry, then turn linked to and carry out Vacuum Deposition conductive metal layer in PVD stove;
2) engineering plastics electronickelling:
Method one: will turn linked to the enterprising electroplating nickel of Electropolating hangers through step 1) engineering plastics product after treatment, first carry out Watt Ni deposition, then carry out semi-bright nickel plating, then by engineering plastics product wire drawing processing, wire drawing product after treatment carries out hydrocarbon vacuum cleaned and oven dry; Or
Method two: will turn linked to the enterprising electroplating nickel of Electropolating hangers through step 1) engineering plastics product after treatment, and first carry out Watt Ni deposition, and then carry out semi-bright nickel plating, then carry out bright nickel plating, and finally carry out microporous nickel plating;
3) by step 2) engineering plastics product after treatment plates PVD corrosion-resistant alloy layer and PVD color layers.
In step 1), described engineering plastic is selected from acrylonitrile-butadiene-styrene (ABS) plastics (ABS), Merlon (PC), Merlon and acrylonitrile-butadiene-phenylethene copolymer alloy (PC/ABS), nylon (PA6/PA66), polyphenylene oxide (PPO), polybutylene terephthalate (PBT) (PBT), polyphenylene oxide, polybutylene terephthalate (PBT), the nylon that glass fibre strengthens, the polybutylene terephthalate (PBT) that glass fibre strengthens, the Merlon that glass fibre strengthens, the one in the nylon that breeze strengthens etc.; Described hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 3～8min, vacuum drying time 5～15min, bake out temperature is 65～120 ℃; Described Vacuum Deposition conductive metal layer is to adopt the mode of magnetron sputtering first to deposit one deck titanium coating, and then sputtering sedimentation layer of metal copper layer.
In step 2) in method one, described Watt Ni deposition, adopts known watt nickel formula to electroplate, the thickness of watt nickel dam is 0.5～3 μ m, then carry out half light nickel and electroplate, adopt known half light nickel formula to electroplate, the thickness of half light nickel dam is 4～14.5 μ m; Described wire drawing processing, can adopt automatic or artificial wire drawing mode to carry out wire drawing, and the rotating speed of wire drawing machine is 600～1200r/min; Pulling wheel can be at least one in nylon wheel, all-wing aircraft wheel etc.; Described hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 3～8min, vacuum drying time 5～15min, bake out temperature is 65～120 ℃;
In step 2) in method two, described Watt Ni deposition, adopt known watt nickel formula to electroplate, the thickness of watt nickel dam is 0.5～2 μ m, then carrying out half light nickel electroplates, adopt known half light nickel formula to electroplate, the thickness of half light nickel dam is 3～6 μ m, then carry out bright nickel plating, adopt known bright nickel formula to electroplate, the thickness of bright nickel layer is 3～6.5 μ m, then carries out microporous nickel plating, adopt known microporous nickel formula to electroplate, the thickness of micropore nickel dam is 0.5～2 μ m.
In step 3), described by step 2) to plate the concrete steps of PVD corrosion-resistant alloy layer and PVD color layers as follows for engineering plastics product after treatment: (1) vacuumizes, when vacuum arrives 2 × 10
-2when Pa, carry out the processing of plasma aura, its technique is ion gun electric current 0.7～1A, bias voltage 150～200V, and dutycycle 20%～50%, argon gas flow velocity 100～200SCCM, time 5～10min, to reach the object of further cleaning; (2) vacuumize, when vacuum arrives (3～9) × 10
-3when Pa, carry out PVD sputter alloy anticorrosion layer, the process conditions of described sputtering sedimentation metal level can be and adopt medium-frequency pulse or dc source, source current 10～50A, sedimentation time 10～40min, bias voltage 120～180V, dutycycle 20%～50%, argon gas flow velocity 60～200SCCM, nitrogen flow rate 0～100SCCM; The target of described PVD alloy anticorrosion layer can adopt zirconium silicon alloy target, at least one in chrome-silicon alloy target material, nichrome target, titanium silicon target etc., or zirconium target and silicon target sputtering sedimentation simultaneously, or chromium target and silicon target sputtering sedimentation simultaneously; Or nickel target and chromium target sputtering sedimentation simultaneously, or titanium target and silicon target sputtering sedimentation simultaneously; (3) after the complete PVD alloy of plated film anticorrosion layer, continue to vacuumize 3～5min, then plate PVD color layers, described its technique of plating PVD color layers is, multi sphere source current 70～120A, sedimentation time 2～5min, bias voltage 80～100V, dutycycle 40%～80%, argon gas flow velocity 20～200SCCM, stream of nitrogen gas speed 0～200SCCM, acetylene gas flow velocity 0～150SCCM, oxygen gas flow velocity 0～150SCCM, the metal targets of described PVD color layers can adopt pure zirconium 99.99%, pure titanium 99.99%, the one in pure chromium 99.99% grade.
Between plating PVD corrosion-resistant alloy layer and PVD color layers, can be coated with PVD plated film transition zone, the plated film time is 1～5min, same according to the plating difference of corrosion-resistant alloy layer, can after PVD plasma aura and between PVD plating corrosion-resistant alloy layer, plate transition zone, the plated film time is 1～5min, adhesion between strengthening each layer of its object and reduce the stress between each layer.
Advantage of the present invention is:
1) having solved current special engineering plastics cannot adopt traditional plating to realize a difficult problem for its surface metalation, avoid chromic harm simultaneously completely, significantly reduce the discharge of electroplating wastewater, electroplated the discharge of wastewater that can save 70%～80% than tradition.
2) PVD coating technique of the present invention makes the performance of product can meet the product corrosion resistance requirement of current bathroom field high-end customer, can pass through according to sanitary ware industry standard:
A, CASS (anti corrosion test ASTM B368-09)-----8h;
B, AASS (salt spray test ASTM G85-9)--------48h.
The specific embodiment
Embodiment 1:
A kind of ABS engineering plastic surface coating structure, its structure starts to be followed successively by vacuum coating (PVD) conductive metal layer from the ABS engineering plastic bed of material, thickness is 0.5 μ m, electroless nickel layer thickness is 15 μ m, PVD corrosion-resistant alloy layer, thickness is 0.5 μ m, corrosion resistant alloy can be zirconium silicon alloy (zirconium silicon atom composition is zirconium 98 silicon 2), PVD color layers, thickness is 0.3 μ m, and color layers is zirconium nitride.
A kind of preparation method of ABS engineering plastic surface coating structure is as follows:
First step ABS engineering plastics vacuum coating PVD pre-metallization: ABS engineering plastics are carried out to hydrocarbon vacuum oil removing and oven dry → PVD plates conductive metal layer; Hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 8min, vacuum drying time 15min, bake out temperature is 65 ℃, PVD plating conductive metal layer is to adopt the mode of magnetron sputtering first to deposit one deck titanium coating, thickness is 0.05 μ m, and then sputtering sedimentation layer of metal copper layer, and thickness is 0.45 μ m.
Second step ABS engineering plastics electronickelling: will turn linked to arriving the enterprising electroplating nickel of Electropolating hangers through first step ABS engineering plastics after treatment product, and carry out according to following technological process:
Carry out Watt Ni deposition → semi-bright nickel → wire drawing processing → hydrocarbon vacuum cleaned and oven dry, wherein Watt Ni deposition, adopt known watt nickel formula to electroplate, the THICKNESS CONTROL of watt nickel is 0.5 μ m, and then carries out half light nickel and electroplate, and adopts known half light nickel formula to electroplate, the THICKNESS CONTROL of half light nickel is at 14.5 μ m, wire drawing processing, can adopt artificial wire drawing mode to carry out wire drawing, and the rotating speed of wire drawing machine is 600r/min; Pulling wheel can be nylon wheel; Then hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 8min, vacuum drying time 15min, bake out temperature is 65 ℃.
The 3rd step is carried out PVD plating corrosion-resistant alloy layer and color layers: ABS engineering plastics electronickelling wire drawing part after treatment second step is suspended on the hanger that PVD plated film uses, and directly hang in PVD stove and carry out PVD plating corrosion-resistant alloy layer and color layers, concrete steps, technique are as follows: (1) vacuumizes, when vacuum arrives 2 × 10
-2when Pa, carry out the processing of plasma aura, its technique is ion gun electric current 0.7A, bias voltage 200V, and dutycycle 20%, argon gas flow velocity 100SCCM, time 5min, to reach the object of further cleaning; (2) vacuumize, when vacuum arrives 9 × 10
-3when Pa, carry out PVD sputter alloy anticorrosion layer, the process conditions of described sputtering sedimentation metal level can be employing dc source, source current 10A, sedimentation time 20min, bias voltage 180V, dutycycle 50%, argon gas flow velocity 200SCCM, the target of described PVD alloy anticorrosion layer can adopt zirconium silicon alloy target.(3) after the complete PVD alloy of plated film anticorrosion layer, continue to vacuumize 3～5min, then plate PVD color layers, described its technique of plating PVD color layers is, multi sphere source current 120A, sedimentation time 5min, bias voltage 80V, dutycycle 40%, argon gas flow velocity 20SCCM, stream of nitrogen gas speed 200SCCM, the metal targets of described PVD color layers can adopt pure zirconium 99.99%.
Testing according to sanitary ware industry standard of the product of the embodiment of the present invention 1:
A, CASS (anti corrosion test ASTM B368-09)-----8h;
B, AASS (salt spray test ASTM G85 9) 48h.
Result shows can be by above-mentioned two testing standards.
Embodiment 2:
A kind of ABS/PC engineering plastic surface coating structure, its structure starts to be followed successively by vacuum coating (PVD) conductive metal layer from the engineering plastic bed of material, thickness is 2 μ m, electroless nickel layer thickness is 7 μ m, PVD corrosion-resistant alloy layer, and thickness is 2 μ m, corrosion resistant alloy can be chrome-silicon alloy (chrome-silicon atomic component is chromium 98 silicon 2), PVD color layers, thickness is 0.1 μ m, color layers is nitrogen zirconium carbide.
A kind of ABS/PC engineering plastic surface coating structure preparation method's implementation step is as follows:
First step ABS/PC engineering plastics vacuum coating PVD pre-metallization: ABS/PC engineering plastics are carried out to hydrocarbon vacuum oil removing and oven dry → PVD plates conductive metal layer; Hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 3min, vacuum drying time 15min, bake out temperature is 65 ℃.Described PVD plating conductive metal layer is to adopt the mode of magnetron sputtering first to deposit one deck titanium coating, and thickness is greater than 0.1 μ m, and then deposition layer of metal copper layer, and thickness is 1.9 μ m.
Second step ABS/PC engineering plastics electronickelling: will turn linked to to the enterprising electroplating nickel of Electropolating hangers through first step ABS/PC engineering plastics after treatment product, and carry out according to following technological process;
Carry out Watt Ni deposition → semi-bright nickel → wire drawing processing → hydrocarbon vacuum cleaned and oven dry, wherein Watt Ni deposition, adopt known watt nickel formula to electroplate, the THICKNESS CONTROL of watt nickel is 3 μ m, and then carries out half light nickel and electroplate, and adopts known half light nickel formula to electroplate, the THICKNESS CONTROL of half light nickel is at 4 μ m, wire drawing processing, can adopt automatic wiredrawing mode to carry out wire drawing, and the rotating speed of wire drawing machine is 1200r/min; Pulling wheel can be all-wing aircraft wheel; Then carry out hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 3min, vacuum drying time 15min, and bake out temperature is 65 ℃.
The 3rd step is carried out PVD plating corrosion-resistant alloy layer and color layers: by ABS/PC engineering plastics wire drawing part after treatment second step and be suspended on the hanger that PVD plated film uses, and directly hang in PVD stove and carry out PVD plating corrosion-resistant alloy layer and color layers; Concrete steps, technique are as follows: (1) vacuumizes, when vacuum arrives 2 × 10
-2when Pa, carry out the processing of plasma aura, its technique is ion gun electric current 1A, bias voltage 150V, and dutycycle 50%, argon gas flow velocity 200SCCM, time 10min, to reach the object of further cleaning; (2) vacuumize, when vacuum arrives 3 × 10
-3when Pa, carry out PVD sputter alloy anticorrosion layer, the process conditions of described sputtering sedimentation metal level can be and adopt medium-frequency pulse power supply, source current 50A, sedimentation time 40min, bias voltage 120V, dutycycle 50%, argon gas flow velocity 200SCCM; The target of described PVD alloy anticorrosion layer can adopt chrome-silicon alloy target material.(3) after the complete PVD alloy of plated film anticorrosion layer, continue to vacuumize 5min, then plate PVD color layers, described its technique of plating PVD color layers is, multi sphere source current 100A, sedimentation time 2min, bias voltage 100V, dutycycle 40%, argon gas flow velocity 20SCCM, stream of nitrogen gas speed 200SCCM, acetylene gas flow velocity 20SCCM, the metal targets of described PVD color layers can adopt pure zirconium 99.99%.
At the interlayer of PVD plating anticorrosion layer and color, also need PVD plated film transition zone according to technological requirement, technique is pulse sputter chrome-silicon alloy; source current 1A; multi sphere plating zirconium, electric current is 100A, sedimentation time 2min; bias voltage 100V; dutycycle 38%, argon gas flow velocity 100SCCM, same according to the plating difference of corrosion-resistant alloy layer; also need after PVD plasma aura and between PVD plating corrosion-resistant alloy layer, plate transition zone, transition zone technique is; D.c. sputtering chromium plating, electric current is 2A, bias voltage 100V, dutycycle 38%, argon gas flow velocity 100SCCM, the plated film time is 5min, adhesion between strengthening each layer of its object and reduce the stress between each layer.
Testing according to sanitary ware industry standard of the product of the embodiment of the present invention 2:
A, CASS (anti corrosion test ASTM B368-09)-----8h;
B, AASS (salt spray test ASTM G85-9)--------48h.
Result shows can both be by above-mentioned two testing standards.
Embodiment 3:
The PA6 engineering plastic surface coating structure that a kind of glass fibre strengthens, its structure starts to be followed successively by vacuum coating (PVD) conductive metal layer from the engineering plastic bed of material, thickness is 1.5 μ m, electroless nickel layer thickness is 10 μ m, PVD corrosion-resistant alloy layer, thickness is 1 μ m, corrosion resistant alloy can be chrome-silicon alloy (chrome-silicon atomic component is chromium 50 silicon 50), PVD color layers, thickness is 0.2 μ m, and color layers is zirconia.
The PA6 engineering plastic surface coating structure preparation method's that a kind of glass fibre strengthens implementation step is as follows:
The PA6 engineering plastics vacuum coating PVD pre-metallization that first step glass fibre strengthens: the PA6 engineering plastics that glass fibre is strengthened carry out hydrocarbon vacuum oil removing and oven dry → PVD plates conductive metal layer; Hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 8min, vacuum drying time 10min, bake out temperature is 120 ℃.Described PVD plating conductive metal layer is to adopt the mode of magnetron sputtering first to deposit one deck titanium coating, and thickness is 0.1 μ m, and then deposition layer of metal copper layer, and thickness is 1.4 μ m.
The PA6 engineering plastics electronickelling that second step glass fibre strengthens: the PA6 engineering plastics product strengthening through first step glass fibre after treatment is turned linked to to the enterprising electroplating nickel of Electropolating hangers, carry out according to following technological process;
Carry out Watt Ni deposition → semi-bright nickel → wire drawing processing → hydrocarbon vacuum cleaned and oven dry, wherein Watt Ni deposition, adopt known watt nickel formula to electroplate, the THICKNESS CONTROL of watt nickel is 3 μ m, and then carries out half light nickel and electroplate, and adopts known half light nickel formula to electroplate, the THICKNESS CONTROL of half light nickel is at 4 μ m, wire drawing processing, can adopt artificial wire drawing mode to carry out wire drawing, and the rotating speed of wire drawing machine is 800r/min; Pulling wheel can be nylon wheel; Then hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 8min, vacuum drying time 10min, bake out temperature is 120 ℃.
The 3rd step is carried out PVD plating corrosion-resistant alloy layer and color layers: the PA6 electronickelling wire drawing part that glass fibre after treatment second step is strengthened is suspended to PVD plated film with on hanger, and directly hangs in PVD stove and carry out PVD plating corrosion-resistant alloy layer and color layers; Concrete steps, technique are as follows: (1) vacuumizes, when vacuum arrives 2 × 10
-2when Pa, carry out the processing of plasma aura, its technique is ion gun electric current 0.8A, bias voltage 180V, and dutycycle 30%, argon gas flow velocity 150SCCM, time 6min, to reach the object of further cleaning; (2) vacuumize, when vacuum arrives 7 × 10
-3when Pa, carry out PVD sputter alloy anticorrosion layer, the process conditions of described sputtering sedimentation metal level can be and adopt medium-frequency pulse and dc source, medium-frequency pulse source current 10A, sputtering target material is pure silicon target, dutycycle 50%, dc source electric current 10A, sputtering target material is pure chromium target, sedimentation time 28min, bias voltage 120, argon gas flow velocity 60SCCM, nitrogen flow rate 100SCCM; (3) after the complete PVD alloy of plated film anticorrosion layer, continue to vacuumize 3min, then plate PVD color layers, described its technique of plating PVD color layers is, multi sphere source current 100A, sedimentation time 2.5min, bias voltage 100V, dutycycle 40%, argon gas flow velocity 50SCCM, oxygen gas flow velocity 150SCCM, the metal targets of described PVD color layers can adopt pure zirconium 99.99%.
At the interlayer of PVD plating anticorrosion layer and color, also need PVD plated film transition zone according to technological requirement, technique is d.c. sputtering chromium; source current 10A; multi sphere plating zirconium, electric current is 100A, sedimentation time 2min; bias voltage 100V; dutycycle 38%, argon gas flow velocity 100SCCM, same according to the plating difference of corrosion-resistant alloy layer; also need after PVD plasma aura and between PVD plating corrosion-resistant alloy layer, plate transition zone, transition zone technique is; DC sputtering deposition chromium, electric current is 5A, bias voltage 100V, dutycycle 38%, argon gas flow velocity 100SCCM, the plated film time is 5min, adhesion between strengthening each layer of its object and reduce the stress between each layer.
Testing according to sanitary ware industry standard of the product of the embodiment of the present invention 3:
A, CASS (anti corrosion test ASTM B368-09)-----8h;
B, AASS (salt spray test ASTM G85-9)--------48h.
Result shows can both be by above-mentioned two testing standards.
Embodiment 4:
Nylon (PA6/PA66) the engineering plastic surface coating structure that a kind of breeze strengthens, its structure starts to be followed successively by vacuum coating (PVD) conductive metal layer from the engineering plastic bed of material, thickness is 1 μ m, electroless nickel layer thickness is 10 μ m, PVD corrosion-resistant alloy layer, thickness is 0.5 μ m, corrosion resistant alloy can be titanium silicon (titanium silicon atom composition is titanium 90 silicon 10), PVD color layers, thickness is 0.3 μ m, and color layers is titanium nitride.
Nylon (PA6/PA66) the engineering plastic surface coating structure preparation method's that a kind of breeze strengthens implementation step is as follows:
Nylon (PA6/PA66) the engineering plastics vacuum coating PVD pre-metallization that first step breeze strengthens: nylon (PA6/PA66) engineering plastics that breeze is strengthened carry out hydrocarbon vacuum oil removing and oven dry → PVD plates conductive metal layer; Hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 5min, vacuum drying time 10min, bake out temperature is 120 ℃.Described PVD plating conductive metal layer is to adopt the mode of magnetron sputtering first to deposit one deck titanium coating, and thickness is 0.1 μ m, and then deposition layer of metal copper layer, and thickness is 0.9 μ m.
Nylon (PA6/PA66) the engineering plastics electronickelling that second step breeze strengthens: nylon (PA6/PA66) the engineering plastics product strengthening through first step breeze after treatment is turned linked to to the enterprising electroplating nickel of Electropolating hangers, carry out according to following technological process;
Carry out Watt Ni deposition → semi-bright nickel → wire drawing processing → hydrocarbon vacuum cleaned and oven dry, wherein Watt Ni deposition, adopt known watt nickel formula to electroplate, the THICKNESS CONTROL of watt nickel is 2 μ m, and then carries out half light nickel and electroplate, and adopts known half light nickel formula to electroplate, the THICKNESS CONTROL of half light nickel is at 8 μ m, then wire drawing processing, can adopt automatic wiredrawing mode to carry out wire drawing, and the rotating speed of wire drawing machine is 800r/min; Pulling wheel can be all-wing aircraft wheel; Then carry out hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 5min, vacuum drying time 10min, and bake out temperature is 120 ℃.
The 3rd step is carried out PVD plating corrosion-resistant alloy layer and color layers: nylon (PA6/PA66) the electronickelling wire drawing part that breeze after treatment second step is strengthened is suspended on the hanger of PVD plated film, and directly hangs in PVD stove and carry out PVD plating corrosion-resistant alloy layer and color layers; Concrete steps, technique are as follows: (1) vacuumizes, when vacuum arrives 2 × 10
-2when Pa, carry out the processing of plasma aura, its technique is ion gun electric current 0.7A, bias voltage 150V, and dutycycle 30%, argon gas flow velocity 150SCCM, time 5min, to reach the object of further cleaning; (2) vacuumize, when vacuum arrives 5 × 10
-3when Pa, carry out PVD sputter alloy anticorrosion layer, the process conditions of described sputtering sedimentation metal level can be employing dc source, source current 30A, sedimentation time 10min, bias voltage 180V, dutycycle 20%, argon gas flow velocity 120SCCM, the target of described PVD alloy anticorrosion layer can adopt titanium silicon target.(3) after the complete PVD alloy of plated film anticorrosion layer, continue to vacuumize 4min, then plate PVD color layers, described its technique of plating PVD color layers is, multi sphere source current 70A, sedimentation time 5min, bias voltage 90V, dutycycle 50%, argon gas flow velocity 100SCCM, stream of nitrogen gas speed 100SCCM, the metal targets of described PVD color layers can adopt pure titanium 99.99%.
Testing according to sanitary ware industry standard of the product of the embodiment of the present invention 4:
A, CASS (anti corrosion test ASTM B368-09)-----8h;
B, AASS (salt spray test ASTM G85-9)--------48h.
Result shows can both be by above-mentioned two testing standards.
Embodiment 5:
A kind of polyphenylene oxide (PPO) engineering plastic surface coating structure, its structure starts to be followed successively by vacuum coating (PVD) conductive metal layer from the engineering plastic bed of material, thickness is 0.8 μ m, electroless nickel layer thickness is 15 μ m, PVD corrosion-resistant alloy layer, and thickness is 0.9 μ m, corrosion resistant alloy can be nichrome (nickel chromium triangle atomic component is nickel 80 chromium 20), PVD color layers, thickness is 0.2 μ m, color layers is pure chromium look.
A kind of polyphenylene oxide (PPO) engineering plastic surface coating structure preparation method's implementation step is as follows:
First step polyphenylene oxide (PPO) engineering plastics vacuum coating PVD pre-metallization: polyphenylene oxide (PPO) engineering plastics are carried out to hydrocarbon vacuum oil removing and oven dry → PVD plates conductive metal layer; Hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 5min, vacuum drying time 8min, bake out temperature is 120 ℃.Described PVD plating conductive metal layer is to adopt the mode of magnetron sputtering first to deposit one deck titanium coating, and thickness is greater than 0.05 μ m, and then deposition layer of metal copper layer, and thickness is 0.85 μ m.
Second step polyphenylene oxide (PPO) engineering plastics electronickelling: will turn linked to to the enterprising electroplating nickel of Electropolating hangers through first step polyphenylene oxide after treatment (PPO) engineering plastics product, and carry out according to following technological process;
Carry out Watt Ni deposition → semi-bright nickel → bright nickel → microporous nickel, wherein Watt Ni deposition, adopt known watt nickel formula to electroplate, the THICKNESS CONTROL of watt nickel is 2 μ m, and then carry out half light nickel and electroplate, adopt known half light nickel formula to electroplate, the THICKNESS CONTROL of half light nickel is at 6 μ m, and then carry out bright nickel plating, and adopt known bright nickel formula to electroplate, the THICKNESS CONTROL of bright nickel is at 6.5 μ m, and then carry out microporous nickel plating, adopt known microporous nickel formula to electroplate, the THICKNESS CONTROL of microporous nickel is at 0.5 μ m
The 3rd step is carried out PVD plating corrosion-resistant alloy layer and color layers: polyphenylene oxide after treatment second step (PPO) plated item is suspended on the hanger that PVD plated film uses, and directly hangs in PVD stove and carry out PVD plating corrosion-resistant alloy layer and color layers; Concrete steps, technique are as follows: (1) vacuumizes, when vacuum arrives 2 × 10
-2when Pa, carry out the processing of plasma aura, its technique is ion gun electric current 1A, bias voltage 150V, and dutycycle 50%, argon gas flow velocity 200SCCM, time 6min, to reach the object of further cleaning; (2) vacuumize, when vacuum arrives 9 × 10
-3when Pa, carry out PVD sputter alloy anticorrosion layer, the process conditions of described sputtering sedimentation metal level can be employing dc source, source current 15A, sedimentation time 40min, bias voltage 180V, dutycycle 50%, argon gas flow velocity 100SCCM, the target of described PVD alloy anticorrosion layer can adopt nichrome target.(3) after the complete PVD alloy of plated film anticorrosion layer, continue to vacuumize 3min, then plate PVD color layers, described its technique of plating PVD color layers is, multi sphere source current 70A, sedimentation time 5min, bias voltage 100V, dutycycle 50%, argon gas flow velocity 120SCCM, the metal targets of described PVD color layers can adopt pure chromium 99.99%.
Testing according to sanitary ware industry standard of the product of the embodiment of the present invention 5:
A, CASS (anti corrosion test ASTM B368-09)-----8h;
B, AASS (salt spray test ASTM G85-9)--------48h.
Result shows can both be by above-mentioned two testing standards.
Embodiment 6:
The PBT engineering plastic surface coating structure that a kind of glass fibre strengthens, its structure starts to be followed successively by vacuum coating (PVD) conductive metal layer from the engineering plastic bed of material, thickness is 1 μ m, electroless nickel layer thickness is 7 μ m, PVD corrosion-resistant alloy layer, thickness is 1 μ m, corrosion resistant alloy can be chrome-silicon alloy (chrome-silicon atomic component is chromium 10 silicon 10), PVD color layers, thickness is 0.3 μ m, and color layers is nitrogen zirconium carbide.
The PBT engineering plastic surface coating structure preparation method's that a kind of glass fibre strengthens implementation step is as follows:
The PBT engineering plastics vacuum coating PVD pre-metallization that first step glass fibre strengthens: the PBT engineering plastics that glass fibre is strengthened carry out hydrocarbon vacuum oil removing and oven dry → PVD plates conductive metal layer; Hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 8min, vacuum drying time 5min, bake out temperature is 120 ℃.Described PVD plating conductive metal layer is to adopt the mode of magnetron sputtering first to deposit one deck titanium coating, and thickness is greater than 0.1 μ m, and then deposition layer of metal copper layer, and thickness is 0.9 μ m.
The PBT engineering plastics electronickelling that second step glass fibre strengthens: the PBT engineering plastics product strengthening through first step glass fibre after treatment is turned linked to to the enterprising electroplating nickel of Electropolating hangers, carry out according to following technological process;
Carry out Watt Ni deposition → semi-bright nickel → bright nickel → microporous nickel, wherein Watt Ni deposition, adopt known watt nickel formula to electroplate, the THICKNESS CONTROL of watt nickel is 0.5 μ m, and then carry out half light nickel and electroplate, adopt known half light nickel formula to electroplate, the THICKNESS CONTROL of half light nickel is at 3 μ m, and then carry out bright nickel plating, and adopt known bright nickel formula to electroplate, the THICKNESS CONTROL of bright nickel is at 3 μ m, and then carry out microporous nickel plating, adopt known microporous nickel formula to electroplate, the THICKNESS CONTROL of microporous nickel is at 0.5 μ m
The 5th step is carried out PVD plating corrosion-resistant alloy layer and color layers: the PBT part that glass fibre after treatment second step is strengthened is suspended on the hanger that PVD plated film uses, and directly hangs in PVD stove and carry out PVD plating corrosion-resistant alloy layer and color layers; Concrete steps, technique are as follows: (1) vacuumizes, when vacuum arrives 2 × 10
-2when Pa, carry out the processing of plasma aura, its technique is ion gun electric current 1A, bias voltage 180V, and dutycycle 40%, argon gas flow velocity 150SCCM, time 7min, to reach the object of further cleaning; (2) vacuumize, when vacuum arrives 6 × 10
-3when Pa, carry out PVD sputter alloy anticorrosion layer, the process conditions of described sputtering sedimentation metal level can be employing dc source, source current 18A, sedimentation time 36min, bias voltage 120V, dutycycle 35%, argon gas flow velocity 100SCCM, the target of described PVD alloy anticorrosion layer can adopt chrome-silicon alloy target material.(3) after the complete PVD alloy of plated film anticorrosion layer, continue to vacuumize 4min, then plate PVD color layers, described its technique of plating PVD color layers is, multi sphere source current 120A, sedimentation time 5min, bias voltage 90V, dutycycle 50%, argon gas flow velocity 50SCCM, stream of nitrogen gas speed 150SCCM, acetylene gas flow velocity 50SCCM, the metal targets of described PVD color layers can adopt pure zirconium 99.99%.
At the interlayer of PVD plating anticorrosion layer and color, also need PVD plated film transition zone according to technological requirement, technique is d.c. sputtering chrome-silicon alloy; source current 2A; multi sphere plating zirconium, electric current is 100A, sedimentation time 3min; bias voltage 100V; dutycycle 38%, argon gas flow velocity 150SCCM, same according to the plating difference of corrosion-resistant alloy layer; also need after PVD plasma aura and between PVD plating corrosion-resistant alloy layer, plate transition zone, transition zone technique is; D.c. sputtering chromium plating, electric current is 2A, bias voltage 100V, dutycycle 38%, argon gas flow velocity 150SCCM, the plated film time is 5min, adhesion between strengthening each layer of its object and reduce the stress between each layer.
Testing according to sanitary ware industry standard of the product of the embodiment of the present invention 6:
A, CASS (anti corrosion test ASTM B368-09)-----8h;
B, AASS (salt spray test ASTM G85-9)--------48h.
Result shows can both be by above-mentioned two testing standards.
Claims (10)
1. an engineering plastic surface coating structure, is characterized in that starting to be followed successively by vacuum coating conductive metal layer, electroless nickel layer, PVD corrosion-resistant alloy layer and PVD color layers from the engineering plastic bed of material; The thickness of described vacuum coating conductive metal layer is 0.5～2 μ m, and the thickness of electroless nickel layer is 7～15 μ m, and the thickness of PVD corrosion-resistant alloy layer is 0.5～2 μ m, and the thickness of PVD color layers is 0.1～0.3 μ m.
2. a kind of engineering plastic surface coating structure as claimed in claim 1, is characterized in that described corrosion resistant alloy is at least one in zirconium silicon alloy, chrome-silicon alloy, nichrome, titanium silicon.
3. a kind of preparation method of engineering plastic surface coating structure as claimed in claim 1, is characterized in that comprising the following steps:
1) engineering plastics vacuum coating PVD pre-metallization: first engineering plastics are carried out to hydrocarbon vacuum oil removing and oven dry, then turn linked to and carry out Vacuum Deposition conductive metal layer in PVD stove;
2) engineering plastics electronickelling:
Method one: will turn linked to the enterprising electroplating nickel of Electropolating hangers through step 1) engineering plastics product after treatment, first carry out Watt Ni deposition, then carry out semi-bright nickel plating, then by engineering plastics product wire drawing processing, wire drawing product after treatment carries out hydrocarbon vacuum cleaned and oven dry; Or
Method two: will turn linked to the enterprising electroplating nickel of Electropolating hangers through step 1) engineering plastics product after treatment, and first carry out Watt Ni deposition, and then carry out semi-bright nickel plating, then carry out bright nickel plating, and finally carry out microporous nickel plating;
3) by step 2) engineering plastics product after treatment plates PVD corrosion-resistant alloy layer and PVD color layers.
4. a kind of preparation method of engineering plastic surface coating structure as claimed in claim 3, it is characterized in that in step 1), described engineering plastic is selected from acrylonitrile-butadiene-styrene (ABS) plastics, Merlon, Merlon and acrylonitrile-butadiene-phenylethene copolymer alloy, nylon, polyphenylene oxide, polybutylene terephthalate (PBT), polyphenylene oxide, polybutylene terephthalate (PBT), the nylon that glass fibre strengthens, the polybutylene terephthalate (PBT) that glass fibre strengthens, the Merlon that glass fibre strengthens, the one in the nylon that breeze strengthens.
5. a kind of preparation method of engineering plastic surface coating structure as claimed in claim 3, it is characterized in that in step 1), described hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 3～8min, vacuum drying time 5～15min, bake out temperature is 65～120 ℃.
6. a kind of preparation method of engineering plastic surface coating structure as claimed in claim 3, it is characterized in that in step 1), described Vacuum Deposition conductive metal layer, adopts the mode of magnetron sputtering first to deposit one deck titanium coating, and then sputtering sedimentation layer of metal copper layer.
7. a kind of preparation method of engineering plastic surface coating structure as claimed in claim 3, it is characterized in that in step 2) in method one, described Watt Ni deposition, adopt known watt nickel formula to electroplate, the thickness of watt nickel dam is 0.5～3 μ m, then carry out half light nickel and electroplate, adopt known half light nickel formula to electroplate, the thickness of half light nickel dam is 4～14.5 μ m; Described wire drawing processing, can adopt automatic or artificial wire drawing mode to carry out wire drawing, and the rotating speed of wire drawing machine is 600～1200r/min; Pulling wheel can be at least one in nylon wheel, all-wing aircraft wheel; Described hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 3～8min, vacuum drying time 5～15min, bake out temperature is 65～120 ℃.
8. a kind of preparation method of engineering plastic surface coating structure as claimed in claim 3, it is characterized in that in step 2) in method two, described Watt Ni deposition, adopt known watt nickel formula to electroplate, the thickness of watt nickel dam is 0.5～2 μ m, then carrying out half light nickel electroplates, adopt known half light nickel formula to electroplate, the thickness of half light nickel dam is 3～6 μ m, then carry out bright nickel plating, adopt known bright nickel formula to electroplate, the thickness of bright nickel layer is 3～6.5 μ m, then carry out microporous nickel plating, adopt known microporous nickel formula to electroplate, the thickness of micropore nickel dam is 0.5～2 μ m.
9. a kind of preparation method of engineering plastic surface coating structure as claimed in claim 3, it is characterized in that in step 3), described by step 2) to plate the concrete steps of PVD corrosion-resistant alloy layer and PVD color layers as follows for engineering plastics product after treatment: (1) vacuumizes, when vacuum arrives 2 × 10
-2when Pa, carry out the processing of plasma aura, its technique is ion gun electric current 0.7～1A, bias voltage 150～200V, and dutycycle 20%～50%, argon gas flow velocity 100～200SCCM, time 5～10min, to reach the object of further cleaning; (2) vacuumize, when vacuum arrives (3～9) × 10
-3when Pa, carry out PVD sputter alloy anticorrosion layer, the process conditions of described sputtering sedimentation metal level can be and adopt medium-frequency pulse or dc source, source current 10～50A, sedimentation time 10～40min, bias voltage 120～180V, dutycycle 20%～50%, argon gas flow velocity 60～200SCCM, nitrogen flow rate 0～100SCCM; The target of described PVD alloy anticorrosion layer can adopt zirconium silicon alloy target, at least one in chrome-silicon alloy target material, nichrome target, titanium silicon target, or zirconium target and silicon target sputtering sedimentation simultaneously, or chromium target and silicon target sputtering sedimentation simultaneously; Or nickel target and chromium target sputtering sedimentation simultaneously, or titanium target and silicon target sputtering sedimentation simultaneously; (3) after the complete PVD alloy of plated film anticorrosion layer, continue to vacuumize 3～5min, then plate PVD color layers, described its technique of plating PVD color layers is, multi sphere source current 70～120A, sedimentation time 2～5min, bias voltage 80～100V, dutycycle 40%～80%, argon gas flow velocity 20～200SCCM, stream of nitrogen gas speed 0～200SCCM, acetylene gas flow velocity 0～150SCCM, oxygen gas flow velocity 0～150SCCM, the metal targets of described PVD color layers can adopt pure zirconium 99.99%, pure titanium 99.99%, the one in pure chromium 99.99%.
10. a kind of preparation method of engineering plastic surface coating structure as claimed in claim 3, it is characterized in that between described PVD corrosion-resistant alloy layer and PVD color layers, be coated with PVD plated film transition zone, the plated film time is 1～5min, after PVD plasma aura and between PVD plating corrosion-resistant alloy layer, plate transition zone, the plated film time is 1～5min.
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