CN103818047B - A kind of engineering plastic surface coating structure and preparation method thereof - Google Patents
A kind of engineering plastic surface coating structure and preparation method thereof Download PDFInfo
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Abstract
A kind of engineering plastic surface coating structure and preparation method thereof, relates to engineering plastic surface and processes。Described engineering plastic surface coating structure, is followed successively by vacuum coating conductive metal layer, electroless nickel layer, PVD corrosion-resistant alloy layer and PVD color layers。First engineering plastics are carried out hydrocarbon vacuum oil removing and drying, then turns linked to and PVD stove carries out Vacuum Deposition conductive metal layer；Being turned linked to Electropolating hangers by engineering plastics product after treatment and carry out electronickelling, first carry out Watt Ni deposition, then carry out semi-bright nickel plating, then engineering plastics product wire drawing processed, the product after wire drawing process carries out hydrocarbon vacuum cleaned and drying；Or engineering plastics product after treatment turned linked to Electropolating hangers carry out electronickelling, first carry out Watt Ni deposition, then carry out semi-bright nickel plating, then carry out bright nickel plating, finally carry out microporous nickel plating；Engineering plastics product after processing is carried out plating PVD corrosion-resistant alloy layer and PVD color layers。
Description
Technical field
The present invention relates to engineering plastic surface to process, particularly to a kind of engineering plastic surface coating structure and preparation method thereof。
Background technology
The plastics being currently used for the industry such as bathroom, household electrical appliances are mainly ABS plastic, or ABS+30%PC plastics, its current surface metalation adopts plating process to carry out, its technical process is: chemistry wax removing oil removing → Cr VI alligatoring → palladium salt absorption → reduction → deposition chemical nickel → electro-coppering → semi-bright nickel → bright nickel → microporous nickel → light chromium, or finally carries out PVD vacuum coating again。Producing substantial amounts of waste water and heavy metal ion in this production procedure, such as environment, the mankind can be produced harm by hexavalent chromium。
The harm of electrodeposited chromium: skin is had by the infringement hexavalent chromium compound of human body skin stimulation and allergy effect。At the position of contact chromate, mist of chromic acid, as hands, wrist, forearm, cervical region etc. are likely to occur dermatitis。Cr VI enters skin through otch and abrasion, can cause chrome ulcer (also known as chrome ulcer) because of corrosiveness。The Cr VI infringement to respiratory system, mainly nasal septum film perforation, pharyngolaryngitis and pneumonia。The infringement Cr VI of internal organs is invaded through digestive tract, taste and smell can be caused to go down, so that disappearing。Dosage h also can corrode internal organs；Cause gastrointestinal function to reduce, stomachache, even intestines and stomach ulcer occur, liver be may also result in harmful effect。The lung of human body is had certain injury by trivalent chromium。It has been experienced that chromic toxicity 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 realizing plastic material is provided, simplify electroplating technology, wastewater discharge is greatly reduced, reduce pollution to environment, and extend electrodepositable plastic rubber substrate scope at plastic rubber substrate surface implementing semi-dry electric plating method。Plastic rubber substrate is carried out anhydrous cleaning and dedusting;Plastic rubber substrate surface is carried out the 1st activation processing；Plastic rubber substrate surface after activation processing is implemented PVD plating bottom, alloy transition layer and metal conducting layer successively process；Plastic rubber substrate after processing is carried out ultrasonic wave water washing and the 2nd activation processing;Plastic rubber substrate Direct Electroplating acid copper after process or immigration nickel bath are implemented nickel plating;Plastic rubber substrate immigration chrome-plating bath after processing is carried out last electrodeposited chromium or turns linked to the deposition carrying out layers of chrome into PVD stove。This patent of invention can carry out PVD stove after electronickelling carry out the deposition of layers of chrome through mentioning, but carries out the example of PVD chromium coating and relevant detailed description after being given at electronickelling from whole patent particularly embodiment part。
There is problems with in the metallization of existing engineering plastic surface, as plating Cr VI can not be got rid of in actual production completely, and cause that environmental protection, producers are produced great harm by it。
Summary of the invention
Present invention aims to the problems referred to above existed in the metallization of existing engineering plastic surface, offer can stop the electrodeposited chromium harm to environment completely, solve electroplating wastewater emission problem simultaneously, electroplating wastewater 70%～80% can be reduced, and there is no 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 μm, and the thickness of electroless nickel layer is 7～15 μm, and the thickness of PVD corrosion-resistant alloy layer is 0.5～2 μm, and the thickness of PVD color layers is 0.1～0.3 μm；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 hydrocarbon vacuum oil removing and drying, then turns linked to and carry out Vacuum Deposition conductive metal layer in PVD stove；
2) engineering plastics electronickelling:
Method one: the engineering plastics product after step 1) processes is turned linked to Electropolating hangers and carries out electronickelling, first carry out Watt Ni deposition, then carrying out semi-bright nickel plating, then engineering plastics product wire drawing processed, the product after wire drawing process carries out hydrocarbon vacuum cleaned and drying；Or
Method two: the engineering plastics product after step 1) processes is turned linked to Electropolating hangers and carries out electronickelling, first carry out Watt Ni deposition, then carry out semi-bright nickel plating, then carry out bright nickel plating, finally carry out microporous nickel plating；
3) by step 2) process after engineering plastics product carry out plating 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 of glass fiber reinforcement, the polybutylene terephthalate (PBT) of glass fiber reinforcement, the Merlon of glass fiber reinforcement, the one in the nylon etc. that breeze strengthens；Described hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 3～8min, vacuum drying time 5～15min, and drying temperature is 65～120 DEG C；Described Vacuum Deposition conductive metal layer is that the mode adopting magnetron sputtering first deposits one layer of titanium coating, then sputtering sedimentation layer of metal layers of copper again。
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 μm, then carrying out half light nickel plating, adopt known half light nickel formula to electroplate, the thickness of half light nickel dam is 4～14.5 μm；Described wire drawing processes, and automatically or manually wire drawing mode can be adopted 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, and drying temperature is 65～120 DEG C；
In step 2) in method two, described Watt Ni deposition, known watt nickel formula is adopted to electroplate, the thickness of watt nickel dam is 0.5～2 μm, then half light nickel plating is carried out, known half light nickel formula is adopted to electroplate, the thickness of half light nickel dam is 3～6 μm, then bright nickel plating is carried out, adopting known bright nickel formula to electroplate, the thickness of bright nickel layer is 3～6.5 μm, then carries out microporous nickel plating, adopting known microporous nickel formula to electroplate, the thickness of micropore nickel dam is 0.5～2 μm。
In step 3), described by step 2) process after engineering plastics product carry out plating PVD corrosion-resistant alloy layer and PVD color layers specifically comprise the following steps that (1) evacuation, when vacuum arrive 2 × 10-2Carrying out plasma glow process during Pa, its technique is ion source electric current 0.7～1A, biases 150～200V, and dutycycle 20%～50%, argon flow velocity 100～200SCCM, time 5～10min, to reach the purpose of further cleaning；(2) evacuation, when vacuum arrives (3～9) × 10-3During Pa, carry out PVD and sputter alloy anticorrosion layer, the process conditions of described sputtering sedimentation metal level can be adopt medium-frequency pulse or DC source, source current 10～50A, sedimentation time 10～40min, biases 120～180V, dutycycle 20%～50%, argon 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 anticorrosion layer of plated film, continue evacuation 3～5min, then plating PVD color layers is carried out, described plating its technique of PVD color layers is, multi sphere source current 70～120A, sedimentation time 2～5min, bias 80～100V, dutycycle 40%～80%, argon 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, PVD plated film transition zone can be coated with, the plated film time is 1～5min, plating also according to corrosion-resistant alloy layer is different, can plate between corrosion-resistant alloy layer, plate transition zone with PVD after PVD plasma glow, the plated film time is 1～5min, and its purpose strengthens the adhesion between each layer and reduces the stress between each layer。
Present invention have an advantage that
1) solving engineering plastics special at present cannot adopt traditional plating to realize a difficult problem for its surface metalation, completely avoid chromic harm simultaneously, drastically reduce the area the discharge of electroplating wastewater, can save the discharge of wastewater of 70%～80% than tradition plating。
2) the PVD coating technique of the present invention makes the performance of product disclosure satisfy that the product corrosion resistance requirement of current bathroom field high-end customer, it is possible to by according to sanitary ware industry standard:
A, CASS (anti corrosion test ASTMB368-09)-----8h；
B, AASS (salt spray test ASTMG85-9)--------48h。
Detailed description of the invention
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 μm, electroless nickel layer thickness is 15 μm, PVD corrosion-resistant alloy layer, thickness is 0.5 μm, and corrosion resistant alloy can be zirconium silicon alloy (zirconium silicon atom composition is zirconium 98 silicon 2), PVD color layers, thickness is 0.3 μm, and color layers is zirconium nitride。
The preparation method of a kind 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 hydrocarbon vacuum oil removing and drying → PVD plates conductive metal layer；Hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 8min, vacuum drying time 15min, drying temperature is 65 DEG C, and it is that the mode adopting magnetron sputtering first deposits one layer of titanium coating that PVD plates conductive metal layer, and thickness is 0.05 μm, then sputtering sedimentation layer of metal layers of copper again, thickness is 0.45 μm。
Second step ABS engineering plastics electronickelling: the ABS engineering plastics product after the first step processes is turned linked to carrying out electronickelling to Electropolating hangers, carries out according to following technological process:
Carry out Watt Ni deposition → semi-bright nickel → wire drawing process → hydrocarbon vacuum cleaned and drying, wherein Watt Ni deposition, known watt nickel formula is adopted to electroplate, the THICKNESS CONTROL of watt nickel is 0.5 μm, then carries out half light nickel plating again, adopts known half light nickel formula to electroplate, the THICKNESS CONTROL of half light nickel is at 14.5 μm, wire drawing processes, and artificial wire drawing mode can be adopted 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, and drying temperature is 65 DEG C。
3rd step carries out PVD and plates corrosion-resistant alloy layer and color layers: the ABS engineering plastics electronickelling wire drawing part after being processed by second step is suspended on the hanger of PVD plated film, and directly hang and in PVD stove, carry out PVD plate corrosion-resistant alloy layer and color layers, concrete steps, technique are as follows: (1) evacuation, when vacuum arrives 2 × 10-2Carrying out plasma glow process during Pa, its technique is ion source electric current 0.7A, biases 200V, and dutycycle 20%, argon flow velocity 100SCCM, time 5min, to reach the purpose of further cleaning；(2) evacuation is carried out, when vacuum arrives 9 × 10-3During Pa, carrying out PVD and sputter alloy anticorrosion layer, the process conditions of described sputtering sedimentation metal level can be adopt DC source, source current 10A, sedimentation time 20min, bias 180V, dutycycle 50%, argon flow velocity 200SCCM, the target of described PVD alloy anticorrosion layer can adopt zirconium silicon alloy target。(3) after the complete PVD alloy anticorrosion layer of plated film, continue evacuation 3～5min, then carrying out plating PVD color layers, described plating its technique of PVD color layers is, multi sphere source current 120A, sedimentation time 5min, bias 80V, dutycycle 40%, argon 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 ASTMB368-09)-----8h；
B, AASS (salt spray test ASTMG85 9) 48h。
Result shows can 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 μm, electroless nickel layer thickness is 7 μm, PVD corrosion-resistant alloy layer, and thickness is 2 μm, corrosion resistant alloy can be chrome-silicon alloy (chrome-silicon atomic component is chromium 98 silicon 2), PVD color layers, thickness is 0.1 μm, and color layers is nitrogen zirconium carbide。
The enforcement step of a kind of ABS/PC engineering plastic surface coating structure preparation method is as follows:
First step ABS/PC engineering plastics vacuum coating PVD pre-metallization: ABS/PC engineering plastics are carried out hydrocarbon vacuum oil removing and drying → PVD plates conductive metal layer；Hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 3min, vacuum drying time 15min, and drying temperature is 65 DEG C。It is that the mode adopting magnetron sputtering first deposits one layer of titanium coating that described PVD plates conductive metal layer, and thickness, more than 0.1 μm, then deposits layer of metal layers of copper again, and thickness is 1.9 μm。
Second step ABS/PC engineering plastics electronickelling: the ABS/PC engineering plastics product after the first step processes is turned linked to carrying out electronickelling to Electropolating hangers, carries out according to following technological process;
Carry out Watt Ni deposition → semi-bright nickel → wire drawing process → hydrocarbon vacuum cleaned and drying, wherein Watt Ni deposition, known watt nickel formula is adopted to electroplate, the THICKNESS CONTROL of watt nickel is 3 μm, then carries out half light nickel plating again, adopts known half light nickel formula to electroplate, the THICKNESS CONTROL of half light nickel is at 4 μm, wire drawing processes, and automatic wiredrawing mode can be adopted to carry out wire drawing, and the rotating speed of wire drawing machine is 1200r/min；Pulling wheel can be taken turns for all-wing aircraft；Then carrying out hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 3min, vacuum drying time 15min, and drying temperature is 65 DEG C。
3rd step carries out PVD and plates corrosion-resistant alloy layer and color layers: ABS/PC engineering plastics wire drawing part after being processed by second step and being suspended on the hanger of PVD plated film, and directly hangs and carry out PVD in PVD stove and plate corrosion-resistant alloy layer and color layers；Concrete steps, technique are as follows: (1) evacuation, when vacuum arrives 2 × 10-2Carrying out plasma glow process during Pa, its technique is ion source electric current 1A, biases 150V, and dutycycle 50%, argon flow velocity 200SCCM, time 10min, to reach the purpose of further cleaning；(2) evacuation is carried out, when vacuum arrives 3 × 10-3During Pa, carrying out PVD and sputter alloy anticorrosion layer, the process conditions of described sputtering sedimentation metal level can be adopt medium-frequency pulse power supply, source current 50A, sedimentation time 40min, biases 120V, dutycycle 50%, argon flow velocity 200SCCM；The target of described PVD alloy anticorrosion layer can adopt chrome-silicon alloy target material。(3) after the complete PVD alloy anticorrosion layer of plated film, continuing evacuation 5min, then carry out plating PVD color layers, described plating its technique of PVD color layers is, multi sphere source current 100A, sedimentation time 2min, biases 100V, dutycycle 40%, argon 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%。
Plating the interlayer of anticorrosion layer and color at PVD, also need PVD plated film transition zone according to technological requirement, technique is pulsed sputter chrome-silicon alloy, source current 1A, multi sphere plating zirconium, electric current is 100A, sedimentation time 2min, bias 100V, dutycycle 38%, argon flow velocity 100SCCM, the plating also according to corrosion-resistant alloy layer is different, also need to plating plate transition zone between corrosion-resistant alloy layer with PVD after PVD plasma glow, transition zone technique is;D.c. sputtering chromium plating, electric current is 2A, biases 100V, dutycycle 38%, argon flow velocity 100SCCM, and the plated film time is 5min, and its purpose strengthens the adhesion between each layer and reduces 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 ASTMB368-09)-----8h；
B, AASS (salt spray test ASTMG85-9)--------48h。
Result shows can both by above-mentioned two testing standards。
Embodiment 3:
A kind of PA6 engineering plastic surface coating structure of glass fiber reinforcement, 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 μm, electroless nickel layer thickness is 10 μm, PVD corrosion-resistant alloy layer, thickness is 1 μm, and corrosion resistant alloy can be chrome-silicon alloy (chrome-silicon atomic component is chromium 50 silicon 50), PVD color layers, thickness is 0.2 μm, and color layers is zirconium oxide。
The enforcement step of the PA6 engineering plastic surface coating structure preparation method of a kind of glass fiber reinforcement is as follows:
The PA6 engineering plastics vacuum coating PVD pre-metallization of first step glass fiber reinforcement: the PA6 engineering plastics of glass fiber reinforcement are carried out hydrocarbon vacuum oil removing and drying → PVD plates conductive metal layer；Hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 8min, vacuum drying time 10min, and drying temperature is 120 DEG C。It is that the mode adopting magnetron sputtering first deposits one layer of titanium coating that described PVD plates conductive metal layer, and thickness is 0.1 μm, then deposits layer of metal layers of copper again, and thickness is 1.4 μm。
The PA6 engineering plastics electronickelling of second step glass fiber reinforcement: the PA6 engineering plastics product of the glass fiber reinforcement after the first step processes is turned linked to carrying out electronickelling to Electropolating hangers, carries out according to following technological process;
Carry out Watt Ni deposition → semi-bright nickel → wire drawing process → hydrocarbon vacuum cleaned and drying, wherein Watt Ni deposition, known watt nickel formula is adopted to electroplate, the THICKNESS CONTROL of watt nickel is 3 μm, then carries out half light nickel plating again, adopts known half light nickel formula to electroplate, the THICKNESS CONTROL of half light nickel is at 4 μm, wire drawing processes, and artificial wire drawing mode can be adopted 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, and drying temperature is 120 DEG C。
3rd step carries out PVD and plates corrosion-resistant alloy layer and color layers: the PA6 electronickelling wire drawing part of the glass fiber reinforcement after being processed by second step is suspended on PVD plated film hanger, and directly hangs and carry out PVD in PVD stove and plate corrosion-resistant alloy layer and color layers；Concrete steps, technique are as follows: (1) evacuation, when vacuum arrives 2 × 10-2Carrying out plasma glow process during Pa, its technique is ion source electric current 0.8A, biases 180V, and dutycycle 30%, argon flow velocity 150SCCM, time 6min, to reach the purpose of further cleaning；(2) evacuation is carried out, when vacuum arrives 7 × 10-3During Pa, carrying out PVD and sputter alloy anticorrosion layer, the process conditions of described sputtering sedimentation metal level can be 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 120, argon flow velocity 60SCCM, nitrogen flow rate 100SCCM；(3) after the complete PVD alloy anticorrosion layer of plated film, continue evacuation 3min, then carrying out plating PVD color layers, described plating its technique of PVD color layers is, multi sphere source current 100A, sedimentation time 2.5min, bias 100V, dutycycle 40%, argon flow velocity 50SCCM, oxygen gas flow velocity 150SCCM, the metal targets of described PVD color layers can adopt pure zirconium 99.99%。
Plating the interlayer of anticorrosion layer and color at PVD, 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 100V, dutycycle 38%, argon flow velocity 100SCCM, the plating also according to corrosion-resistant alloy layer is different, also need to plating plate transition zone between corrosion-resistant alloy layer with PVD after PVD plasma glow, transition zone technique is;DC sputtering deposition chromium, electric current is 5A, biases 100V, dutycycle 38%, argon flow velocity 100SCCM, and the plated film time is 5min, and its purpose strengthens the adhesion between each layer and reduces 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 ASTMB368-09)-----8h；
B, AASS (salt spray test ASTMG85-9)--------48h。
Result shows can both 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 μm, electroless nickel layer thickness is 10 μm, PVD corrosion-resistant alloy layer, thickness is 0.5 μm, and corrosion resistant alloy can be titanium silicon (titanium silicon atom composition is titanium 90 silicon 10), PVD color layers, thickness is 0.3 μm, and color layers is titanium nitride。
The enforcement step of nylon (PA6/PA66) the engineering plastic surface coating structure preparation method that a kind of breeze strengthens 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 strengthens are carried out hydrocarbon vacuum oil removing and drying → PVD plates conductive metal layer；Hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 5min, vacuum drying time 10min, and drying temperature is 120 DEG C。It is that the mode adopting magnetron sputtering first deposits one layer of titanium coating that described PVD plates conductive metal layer, and thickness is 0.1 μm, then deposits layer of metal layers of copper again, and thickness is 0.9 μm。
Nylon (PA6/PA66) the engineering plastics electronickelling that second step breeze strengthens: nylon (PA6/PA66) the engineering plastics product that the breeze after the first step processes strengthens is turned linked to carrying out electronickelling to Electropolating hangers, carries out according to following technological process;
Carry out Watt Ni deposition → semi-bright nickel → wire drawing process → hydrocarbon vacuum cleaned and drying, wherein Watt Ni deposition, known watt nickel formula is adopted to electroplate, the THICKNESS CONTROL of watt nickel is 2 μm, then carries out half light nickel plating again, adopts known half light nickel formula to electroplate, the THICKNESS CONTROL of half light nickel is at 8 μm, then wire drawing processes, and automatic wiredrawing mode can be adopted to carry out wire drawing, and the rotating speed of wire drawing machine is 800r/min；Pulling wheel can be taken turns for all-wing aircraft；Then carrying out hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 5min, vacuum drying time 10min, and drying temperature is 120 DEG C。
3rd step carries out PVD and plates corrosion-resistant alloy layer and color layers: nylon (PA6/PA66) the electronickelling wire drawing part that the breeze after being processed by second step strengthens is suspended on the hanger of PVD plated film, and directly hangs and carry out PVD in PVD stove and plate corrosion-resistant alloy layer and color layers；Concrete steps, technique are as follows: (1) evacuation, when vacuum arrives 2 × 10-2Carrying out plasma glow process during Pa, its technique is ion source electric current 0.7A, biases 150V, and dutycycle 30%, argon flow velocity 150SCCM, time 5min, to reach the purpose of further cleaning；(2) evacuation is carried out, when vacuum arrives 5 × 10-3During Pa, carrying out PVD and sputter alloy anticorrosion layer, the process conditions of described sputtering sedimentation metal level can be adopt DC source, source current 30A, sedimentation time 10min, bias 180V, dutycycle 20%, argon flow velocity 120SCCM, the target of described PVD alloy anticorrosion layer can adopt titanium silicon target。(3) after the complete PVD alloy anticorrosion layer of plated film, continue evacuation 4min, then carrying out plating PVD color layers, described plating its technique of PVD color layers is, multi sphere source current 70A, sedimentation time 5min, bias 90V, dutycycle 50%, argon 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 ASTMB368-09)-----8h；
B, AASS (salt spray test ASTMG85-9)--------48h。
Result shows can both 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 μm, electroless nickel layer thickness is 15 μm, PVD corrosion-resistant alloy layer, and thickness is 0.9 μm, corrosion resistant alloy can be nichrome (nickel chromium triangle atomic component is nickel 80 chromium 20), PVD color layers, thickness is 0.2 μm, and color layers is pure chromium color。
The enforcement step of a kind of polyphenylene oxide (PPO) engineering plastic surface coating structure preparation method is as follows:
First step polyphenylene oxide (PPO) engineering plastics vacuum coating PVD pre-metallization: polyphenylene oxide (PPO) engineering plastics are carried out hydrocarbon vacuum oil removing and drying → PVD plates conductive metal layer；Hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 5min, vacuum drying time 8min, and drying temperature is 120 DEG C。It is that the mode adopting magnetron sputtering first deposits one layer of titanium coating that described PVD plates conductive metal layer, and thickness, more than 0.05 μm, then deposits layer of metal layers of copper again, and thickness is 0.85 μm。
Second step polyphenylene oxide (PPO) engineering plastics electronickelling: polyphenylene oxide (PPO) the engineering plastics product after the first step processes is turned linked to carrying out electronickelling to Electropolating hangers, carries out according to following technological process;
Carry out Watt Ni deposition → semi-bright nickel → bright nickel → microporous nickel, wherein Watt Ni deposition, known watt nickel formula is adopted to electroplate, the THICKNESS CONTROL of watt nickel is 2 μm, then half light nickel plating is carried out again, known half light nickel formula is adopted to electroplate, the THICKNESS CONTROL of half light nickel is at 6 μm, then carrying out bright nickel plating again, adopt known bright nickel formula to electroplate, the THICKNESS CONTROL of bright nickel is at 6.5 μm, then microporous nickel plating is carried out again, adopting known microporous nickel formula to electroplate, the THICKNESS CONTROL of microporous nickel is at 0.5 μm
3rd step carries out PVD and plates corrosion-resistant alloy layer and color layers: polyphenylene oxide (PPO) plated item after being processed by second step is suspended on the hanger of PVD plated film, and directly hangs and carry out PVD in PVD stove and plate corrosion-resistant alloy layer and color layers；Concrete steps, technique are as follows: (1) evacuation, when vacuum arrives 2 × 10-2Carrying out plasma glow process during Pa, its technique is ion source electric current 1A, biases 150V, and dutycycle 50%, argon flow velocity 200SCCM, time 6min, to reach the purpose of further cleaning；(2) evacuation is carried out, when vacuum arrives 9 × 10-3During Pa, carrying out PVD and sputter alloy anticorrosion layer, the process conditions of described sputtering sedimentation metal level can be adopt DC source, source current 15A, sedimentation time 40min, bias 180V, dutycycle 50%, argon flow velocity 100SCCM, the target of described PVD alloy anticorrosion layer can adopt nichrome target。(3) after the complete PVD alloy anticorrosion layer of plated film, continue evacuation 3min, then plating PVD color layers is carried out, described plating its technique of PVD color layers is, multi sphere source current 70A, sedimentation time 5min, bias 100V, dutycycle 50%, argon 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 ASTMB368-09)-----8h；
B, AASS (salt spray test ASTMG85-9)--------48h。
Result shows can both by above-mentioned two testing standards。
Embodiment 6:
A kind of PBT engineering plastic surface coating structure of glass fiber reinforcement, its structure starts to be followed successively by vacuum coating (PVD) conductive metal layer from the engineering plastic bed of material, thickness is 1 μm, electroless nickel layer thickness is 7 μm, PVD corrosion-resistant alloy layer, thickness is 1 μm, and corrosion resistant alloy can be chrome-silicon alloy (chrome-silicon atomic component is chromium 10 silicon 10), PVD color layers, thickness is 0.3 μm, and color layers is nitrogen zirconium carbide。
The enforcement step of the PBT engineering plastic surface coating structure preparation method of a kind of glass fiber reinforcement is as follows:
The PBT engineering plastics vacuum coating PVD pre-metallization of first step glass fiber reinforcement: the PBT engineering plastics of glass fiber reinforcement are carried out hydrocarbon vacuum oil removing and drying → PVD plates conductive metal layer；Hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 8min, vacuum drying time 5min, and drying temperature is 120 DEG C。It is that the mode adopting magnetron sputtering first deposits one layer of titanium coating that described PVD plates conductive metal layer, and thickness, more than 0.1 μm, then deposits layer of metal layers of copper again, and thickness is 0.9 μm。
The PBT engineering plastics electronickelling of second step glass fiber reinforcement: the PBT engineering plastics product of the glass fiber reinforcement after the first step processes is turned linked to carrying out electronickelling to Electropolating hangers, carries out according to following technological process；
Carry out Watt Ni deposition → semi-bright nickel → bright nickel → microporous nickel, wherein Watt Ni deposition, known watt nickel formula is adopted to electroplate, the THICKNESS CONTROL of watt nickel is 0.5 μm, then half light nickel plating is carried out again, known half light nickel formula is adopted to electroplate, the THICKNESS CONTROL of half light nickel is at 3 μm, then carrying out bright nickel plating again, adopt known bright nickel formula to electroplate, the THICKNESS CONTROL of bright nickel is at 3 μm, then microporous nickel plating is carried out again, adopting known microporous nickel formula to electroplate, the THICKNESS CONTROL of microporous nickel is at 0.5 μm
5th step carries out PVD and plates corrosion-resistant alloy layer and color layers: the PBT part of the glass fiber reinforcement after being processed by second step is suspended on the hanger of PVD plated film, and directly hangs and carry out PVD in PVD stove and plate corrosion-resistant alloy layer and color layers；Concrete steps, technique are as follows: (1) evacuation, when vacuum arrives 2 × 10-2Carrying out plasma glow process during Pa, its technique is ion source electric current 1A, biases 180V, and dutycycle 40%, argon flow velocity 150SCCM, time 7min, to reach the purpose of further cleaning；(2) evacuation is carried out, when vacuum arrives 6 × 10-3During Pa, carrying out PVD and sputter alloy anticorrosion layer, the process conditions of described sputtering sedimentation metal level can be adopt DC source, source current 18A, sedimentation time 36min, bias 120V, dutycycle 35%, argon flow velocity 100SCCM, the target of described PVD alloy anticorrosion layer can adopt chrome-silicon alloy target material。(3) after the complete PVD alloy anticorrosion layer of plated film, continuing evacuation 4min, then carry out plating PVD color layers, described plating its technique of PVD color layers is, multi sphere source current 120A, sedimentation time 5min, biases 90V, dutycycle 50%, argon 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%。
Plating the interlayer of anticorrosion layer and color at PVD, 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 100V, dutycycle 38%, argon flow velocity 150SCCM, the plating also according to corrosion-resistant alloy layer is different, also need to plating plate transition zone between corrosion-resistant alloy layer with PVD after PVD plasma glow, transition zone technique is;D.c. sputtering chromium plating, electric current is 2A, biases 100V, dutycycle 38%, argon flow velocity 150SCCM, and the plated film time is 5min, and its purpose strengthens the adhesion between each layer and reduces 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 ASTMB368-09)-----8h；
B, AASS (salt spray test ASTMG85-9)--------48h。
Result shows can both by above-mentioned two testing standards。
Claims (11)
1. an engineering plastic surface coating structure, it is characterised in that start 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 μm, and the thickness of electroless nickel layer is 7～15 μm, and the thickness of PVD corrosion-resistant alloy layer is 0.5～2 μm, and the thickness of PVD color layers is 0.1～0.3 μm。
2. a kind of engineering plastic surface coating structure as claimed in claim 1, it is characterised in that described corrosion resistant alloy is at least one in zirconium silicon alloy, chrome-silicon alloy, nichrome, titanium silicon。
3. the preparation method of a kind of engineering plastic surface coating structure as claimed in claim 1, it is characterised in that comprise the following steps:
1) engineering plastics vacuum coating PVD pre-metallization: first engineering plastics are carried out hydrocarbon vacuum oil removing and drying, then turns linked to and carry out Vacuum Deposition conductive metal layer in PVD stove；
2) engineering plastics electronickelling:
Method one: by through step 1) process after engineering plastics product turn linked to Electropolating hangers and carry out electronickelling, first carry out Watt Ni deposition, then carrying out semi-bright nickel plating, then engineering plastics product wire drawing processed, the product after wire drawing process carries out hydrocarbon vacuum cleaned and drying；Or
Method two: by through step 1) process after engineering plastics product turn linked to Electropolating hangers and carry out electronickelling, first carry out Watt Ni deposition, then carry out semi-bright nickel plating, then carry out bright nickel plating, finally carry out microporous nickel plating；
3) by step 2) process after engineering plastics product carry out plating PVD corrosion-resistant alloy layer and PVD color layers。
4. the preparation method of a kind of engineering plastic surface coating structure as claimed in claim 3, it is characterized in that in step 1) in, described engineering plastics are selected from acrylonitrile-butadiene-styrene (ABS) plastics, Merlon, Merlon and acrylonitrile-butadiene-phenylethene copolymer alloy, nylon, polyphenylene oxide, the one in polybutylene terephthalate (PBT)。
5. the preparation method of a kind of engineering plastic surface coating structure as claimed in claim 4, it is characterised in that described nylon is selected from the nylon of glass fiber reinforcement or the nylon of breeze enhancing；Described polybutylene terephthalate (PBT) is the polybutylene terephthalate (PBT) of glass fiber reinforcement；Described Merlon is the Merlon of glass fiber reinforcement。
6. the preparation method of a kind of engineering plastic surface coating structure as claimed in claim 3, it is characterized in that in step 1) in, described hydrocarbon vacuum oil removing and drying and processing, the oil removing time is 3～8min, vacuum drying time 5～15min, drying temperature is 65～120 DEG C。
7. the preparation method of a kind of engineering plastic surface coating structure as claimed in claim 3, it is characterized in that in step 1) in, described Vacuum Deposition conductive metal layer, adopts the mode of magnetron sputtering first to deposit one layer of titanium coating, then sputtering sedimentation layer of metal layers of copper again。
8. the preparation method of a kind 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, known watt nickel formula is adopted to electroplate, the thickness of watt nickel dam is 0.5～3 μm, then carrying out half light nickel plating, adopt known half light nickel formula to electroplate, the thickness of half light nickel dam is 4～14.5 μm；Described wire drawing processes, and adopts automatically or manually wire drawing mode to carry out wire drawing, and the rotating speed of wire drawing machine is 600～1200r/min；Pulling wheel is 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, and drying temperature is 65～120 DEG C。
9. the preparation method of a kind 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, known watt nickel formula is adopted to electroplate, the thickness of watt nickel dam is 0.5～2 μm, then half light nickel plating is carried out, known half light nickel formula is adopted to electroplate, the thickness of half light nickel dam is 3～6 μm, then bright nickel plating is carried out, known bright nickel formula is adopted to electroplate, the thickness of bright nickel layer is 3～6.5 μm, then microporous nickel plating is carried out, known microporous nickel formula is adopted to electroplate, the thickness of micropore nickel dam is 0.5～2 μm。
10. the preparation method of a kind of engineering plastic surface coating structure as claimed in claim 9, it is characterized in that in step 3) in, described by step 2) process after engineering plastics product carry out plating PVD corrosion-resistant alloy layer and PVD color layers specifically comprise the following steps that (1) evacuation, when vacuum arrive 2 × 10-2Carrying out plasma glow process during Pa, its technique is ion source electric current 0.7～1A, biases 150～200V, and dutycycle 20%～50%, argon flow velocity 100～200SCCM, time 5～10min, to reach the purpose of further cleaning；(2) evacuation, when vacuum arrives (3～9) × 10-3During Pa, carry out PVD and sputter corrosion-resistant alloy layer, the process conditions of described sputtering sedimentation metal level are for adopting medium-frequency pulse or DC source, source current 10～50A, sedimentation time 10～40min, biases 120～180V, dutycycle 20%～50%, argon flow velocity 60～200SCCM, nitrogen flow rate 0～100SCCM；The target of described PVD corrosion-resistant alloy layer adopts at least one in zirconium silicon alloy target, 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 corrosion-resistant alloy layer of plated film, continue evacuation 3～5min, then plating PVD color layers is carried out, described plating its technique of PVD color layers is, multi sphere source current 70～120A, sedimentation time 2～5min, bias 80～100V, dutycycle 40%～80%, argon flow velocity 20～200SCCM, nitrogen flow rate 0～200SCCM, acetylene gas flow velocity 0～150SCCM, oxygen gas flow rate 0～150SCCM, the metal targets of described PVD color layers adopts pure zirconium 99.99%, pure titanium 99.99%, the one in pure chromium 99.99%。
11. the preparation method of a kind of engineering plastic surface coating structure as claimed in claim 10, it is characterized in that between described PVD corrosion-resistant alloy layer and PVD color layers, it is coated with PVD plated film transition zone, the plated film time is 1～5min, plating plate transition zone between corrosion-resistant alloy layer with PVD after PVD plasma glow, the plated film time is 1～5min。
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| CN106086790B (en) * | 2016-06-08 | 2018-10-12 | 宁波威霖住宅设施有限公司 | A kind of kirsite antique copper vacuum coating method |
| CN106283051B (en) * | 2016-08-08 | 2019-04-19 | 惠州建邦精密塑胶有限公司 | Composite structure and preparation method thereof |
| CN107557830A (en) * | 2017-09-11 | 2018-01-09 | 江阴市羽项汽车饰件有限公司 | A kind of double-colored electroplating technology |
| CN107740056B (en) * | 2017-09-30 | 2018-10-30 | 宁波塑金真空科技有限公司 | The preparation method of anlistatig vacuum-coated piece |
| CN113529020A (en) * | 2021-07-13 | 2021-10-22 | 鄂州市金瑞康电子工具科技有限公司 | Anticorrosive and antirust treatment process on iron-based material and anticorrosive and antirust coating |
| CN113718251A (en) * | 2021-08-25 | 2021-11-30 | 深圳市金源康实业有限公司 | Plastic surface coating structure and preparation method thereof |
| CN115287587A (en) * | 2022-07-21 | 2022-11-04 | 厦门建霖健康家居股份有限公司 | Method for plating wire drawing film on plastic substrate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1268535A (en) * | 1999-03-01 | 2000-10-04 | 莫恩股份有限公司 | Corrosion resistance and wear-resistance decoration coatings |
| CN101343724A (en) * | 2008-08-15 | 2009-01-14 | 厦门建霖工业有限公司 | Method for functional decoration film coating on engineering plastic rubber surface |
| CN102127764A (en) * | 2011-01-28 | 2011-07-20 | 厦门建霖工业有限公司 | Method for implementing semi-dry plating on surface of plastic substrate |
| CN102605398A (en) * | 2012-04-13 | 2012-07-25 | 广州摩恩水暖器材有限公司 | Method for treating surface of faucet |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008046673A1 (en) * | 2008-09-10 | 2010-03-11 | Grohe Ag | composite body |
-
2014
- 2014-02-28 CN CN201410072411.1A patent/CN103818047B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1268535A (en) * | 1999-03-01 | 2000-10-04 | 莫恩股份有限公司 | Corrosion resistance and wear-resistance decoration coatings |
| CN101343724A (en) * | 2008-08-15 | 2009-01-14 | 厦门建霖工业有限公司 | Method for functional decoration film coating on engineering plastic rubber surface |
| CN102127764A (en) * | 2011-01-28 | 2011-07-20 | 厦门建霖工业有限公司 | Method for implementing semi-dry plating on surface of plastic substrate |
| CN102605398A (en) * | 2012-04-13 | 2012-07-25 | 广州摩恩水暖器材有限公司 | Method for treating surface of faucet |
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