CN104694896A - Surface treatment method for heavy anticorrosive bolt - Google Patents
Surface treatment method for heavy anticorrosive bolt Download PDFInfo
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- CN104694896A CN104694896A CN201510078399.XA CN201510078399A CN104694896A CN 104694896 A CN104694896 A CN 104694896A CN 201510078399 A CN201510078399 A CN 201510078399A CN 104694896 A CN104694896 A CN 104694896A
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Abstract
The invention relates to a surface treatment method for a heavy anticorrosive bolt. The treatment process comprises the following steps that a first protective film is constructed on the surface of a bolt workpiece by virtue of a magnetron sputtering technology, wherein the first protective film is formed by alternatively laminating a Cr layer and a Cr(N) layer on the surface of the bolt workpiece, a pure Cr film has a dense fiber tissue structure, the Cr(N) layer has a good void-free structure, generation of columnar crystals of the pure Cr film can be retarded, voids caused by the columnar crystals of the pure Cr layer can be well filled, and the corrosion resistance of the bolt workpiece is preliminarily improved; and a second protective film is constructed outside the first protective film, and because a polymer monomer methyl methacrylate is small in size and easily enters the defects and gaps on the surface of the bolt, due to catalysis of azodiisobutyronitrile, the methyl methacrylate is polymerized and cured in the defects and gaps of the first protective film, the defects and gaps on the surface of the bolt are filled, and good anticorrosive performance of the bolt workpiece is further ensured.
Description
Technical field
The present invention relates to heavy antisepsis treatment process technical field, specifically refer to a kind of surface treatment method of heavy antisepsis bolt.
Background technology
In daily life and industrial production manufacture, bolt is absolutely necessary mechanical component, and it is called as the rice of industry, is widely used in electronic product, engineering goods, digital product, power equipment, electronic product, boats and ships, vehicle, hydro project, even chemical experiment is upper.Bolt in use, often causes because of the problem such as burn into friction, wearing and tearing on bolt surface losing efficacy or destroying, thus affects the work-ing life of bolt, even bring more serious potential safety hazard.Especially in the occasion that envrionment conditions is harsher, the protection of bolt is had higher requirement.
Traditional surface protection technique utilizes plating, chemical plating method plating protection film at workpiece surface, but the film obtained and workpiece substrate are in conjunction with poor, and the waste liquid produced in plating process can to causing severe environmental pollution.Magnetron sputtering is a kind of eco-friendly physical gas phase deposition technology, is one of method for manufacturing thin film having development prospect, and this technology is increasingly extensive to be applied in the preparation field of workpiece substrate surfacecti proteon film.The film utilizing magnetron sputtering technique to prepare has following advantage: (1) is pollution-free; (2) deposit the smooth densification of film surface obtained, thickness is even, controllability good; (3) film and substrate combinating strength high.But, due to by the shade influence in magnetron sputtering deposition process and low atomic migration capabilities limits, the film that magnetron sputtering deposition obtains is often for having the columnar crystal structure of more intercrystal pore, and the space between column crystal easily becomes the weak location of film protection, corrosive fluid arrives matrix by these space rapid diffusion, thus causes film to the corrosion prevention effect premature failure of matrix.
Therefore, for the process of surface treatment of current heavy antisepsis bolt, await doing further improvement.
Summary of the invention
Technical problem to be solved by this invention is the surface treatment method providing a kind of heavy antisepsis bolt for the above-mentioned state of the art, this technique can form on bolt surface the protection film that layer of surface is smooth, density is high, film-substrate cohesion is high, effectively improves the antiseptic property of bolt.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of surface treatment method of heavy antisepsis bolt, is characterized in that comprising the following steps:
(1) pre-treatment of bolt workpiece
A, bolt workpiece to be immersed in chemical alkali lye completely, after being heated to 70 ~ 80 DEG C, in ultrasonic cleaner, to clean 20 ~ 60min; Take out bolt workpiece, remove the chemical alkali lye of bolt workpiece surface with the cleaning of pure water;
B, the bolt workpiece after a process is immersed in mass concentration is completely in the hydrochloric acid soln of 5 ~ 15wt%, cleans 5 ~ 15min under room temperature in ultrasonic cleaner; Take out bolt workpiece, remove the hydrochloric acid soln of bolt workpiece surface with the cleaning of pure water;
C, the bolt workpiece after b process is immersed in ethanol or acetone completely, in ultrasonic cleaner, cleans 20 ~ 30min under room temperature, take out for subsequent use;
The structure of (2) first protective films
Adopt magnetron sputtering technique to build the first protective film at bolt workpiece surface, concrete steps comprise:
A, to be greater than in vacuum indoor location purity 98% chromium target, make the angle of chromium target head and horizontal plane between 45 ° ~ 90 °; Bolt workpiece is placed on the work rest in vacuum chamber, vacuumizes, make the vacuum tightness in vacuum chamber be less than or equal to 1 × 10
-3pa; Employing rare gas element is working gas, cleans workpiece surface with ion source, and the air pressure range regulating ion source work is 2 × 10
-2~ 7 × 10
-2pa, power is 100 ~ 150W, and scavenging period is 10 ~ 50min;
B, employing rare gas element are working gas, carry out sputtering sedimentation Cr film to bolt workpiece, and operating air pressure is 0.1 ~ 10Pa, and unit target sputtering power is 1 ~ 5W/cm
2, adopt at least one sputtering palladium to carry out sputtering sedimentation Cr film to bolt workpiece, sputtering time is 100 ~ 1500s;
The mixed gas of c, employing nitrogen and rare gas element is working gas, and carry out sputtering sedimentation Cr (N) film to bolt workpiece, operating air pressure is 0.1 ~ 10Pa, and unit target sputtering power is 1 ~ 5W/cm
2, adopt at least one sputtering palladium to carry out sputtering sedimentation Cr (N) film to bolt workpiece, sputtering time is 100 ~ 1500s;
D, successively repeating step b, step c 5 ~ 25 times, make pure Cr layer and Cr (N) layer at the multi-layer film structure of the alternately laminated formation periodic arrangement of bolt workpiece surface;
(3) thermal treatment of bolt workpiece
Step (2) gained bolt workpiece is placed in retort furnace, and arranging heat-up rate is 5 ~ 10 DEG C/min, is incubated 1 ~ 3h, then furnace cooling after being warming up to 500 ~ 600 DEG C;
The structure of (4) second protective films
It is in the methanol solution of the methyl methacrylate of 3 ~ 8% that step (3) gained bolt workpiece is immersed in mass concentration, and Diisopropyl azodicarboxylate is added in this solution, the quality of this Diisopropyl azodicarboxylate is made to be 0.1 ~ 0.3% of methyl methacrylate quality, then at 50 ~ 60 DEG C, leave standstill 6 ~ 8h, take out and dry.
As a further improvement on the present invention, chemical alkali lye described in step (1) comprises sodium hydroxide, sodium phosphate, water glass, sulphonic acids tensio-active agent and deionized water, and the concentration of described sodium hydroxide, sodium phosphate, water glass, sulphonic acids tensio-active agent is respectively 10 ~ 15g/L, 60 ~ 70g/L, 10 ~ 15g/L, 0.1 ~ 0.5wt%.Wherein, sodium hydroxide is a kind of highly basic, has very strong saponifying ability, reacts can generate water-soluble sodium soap with saponified oil; Sodium phosphate has good deoiling effect and shock absorption, and itself washing property is good, also has certain emulsifying capacity in addition; Water glass has good surfactivity and certain saponifying ability, is best wetting agent, one of emulsifying agent and dispersion agent in alkaloid compound; Tensio-active agent can remove non-soap carburetion, containing hydrophilic radical and hydrophobic group in the molecular structure of tensio-active agent, hydrophobic group is adsorbed on oil with on the interface of solution, hydrophilic radical combines with water, under the effect that surfactant molecule aligns, the surface tension of oil-solution interface can reduce, and under the effect such as solution convection current and stirring, greasy dirt just can be easy to depart from piece surface.
As preferably, described sulphonic acids tensio-active agent is the one in sulphosuccinates, alkylbenzene sulfonate, alkylsulfonate, α olefin sulfonate.
As preferably, described rare gas element is the one in helium, neon, argon gas, Krypton.
Further improvement, after a step terminates in described step (2), before b step starts, regulating fender is relative with chromium target, and the power supply that unlatching chromium target is corresponding carries out pre-sputtering 5 ~ 30min.Adopt such process, can the impurity on chromium target surface and other pollutents be sputtered on baffle plate, to improve the film purity being splashed to bolt workpiece substrate surface.
Further, in described step (2) step c, the throughput ratio of nitrogen and rare gas element is 4 ~ 6: 10.Under this throughput ratio, the major ingredient of coating is Cr
2n, and containing a small amount of pure Cr and CrN, thus on the basis of eliminating Cr layer columnar crystal structure, Cr film and Cr (N) film are organically combined, strengthen the antiseptic property of bolt workpiece further.
Preferably, described step utilizes ion source to provide ion beam assisted depositing in (2), and ion source operating voltage is 140 ~ 160V, and working current is 0.7 ~ 1.2A; Utilize additional power source hot donut, vacuum room temp is 50 ~ 300 DEG C; Utilize additional power source between work rest and vacuum chamber, apply the bias voltage of 0 ~ 400V.
In such scheme, the first protective film thickness of step (2) gained bolt workpiece surface is 4 ~ 15 μm.
Compared with prior art, the invention has the advantages that:
(1) plate Cr film, to body material, there is good adhesion, can effectively improve resistance to wearing of body material, Corrosion Protection, the present invention adopts the method for magnetron sputtering to be coated with Cr film and Cr (N) film of alternating deposit at bolt workpiece surface, pure Cr film has intensive fibrous tissue structure, and Cr (N) layer has good tight structure, the generation of slow pure Cr film column crystal can not only be hindered, the space caused due to pure Cr layer columnar crystal structure can also be filled up preferably, formation layer of surface is smooth, density is high, the first protective film that film-substrate cohesion is high, tentatively improve bolt workpiece Corrosion Protection,
(2) major ingredient of Cr (N) film is Cr
2n, and containing a small amount of pure Cr and CrN, thus on the basis of eliminating Cr layer columnar crystal structure, Cr film and Cr (N) film can be organically combined, strengthen the antiseptic property of bolt workpiece further;
(3) by magnetron sputtering after bolt workpiece surface forms the first protective film be made up of Cr film and Cr (N) film, the second finer and closely woven protective film is constructed again on bolt surface, due to polymer monomer methyl methacrylate small volume, be easy to enter in the defect on bolt surface, gap, and, by the catalysis of Diisopropyl azodicarboxylate, methyl methacrylate is polymerizing curable in the defect, gap of the first protective film, the defect on bolt surface, gap are filled up, further ensure that bolt workpiece has good antiseptic property;
(4) after structure first protective film, build the second protective film before heat-treat, the bonding force between the first protective film and bolt workpiece substrate can be increased, improve surface hardness and the rub resistance power of the first protective film, eliminate unrelieved stress.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1:
The surface treatment method of the heavy antisepsis bolt of the present embodiment comprises the following steps:
(1) pre-treatment of bolt workpiece
A, bolt workpiece to be immersed in chemical alkali lye completely, after being heated to 70 DEG C, in ultrasonic cleaner, to clean 60min; Take out bolt workpiece, remove the chemical alkali lye of bolt workpiece surface with the cleaning of pure water;
Above-mentioned chemical alkali lye comprises sodium hydroxide, sodium phosphate, water glass, alkyl diphenyl base oxide stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate (DOWFAX 2A1) and deionized water, wherein, the concentration of sodium hydroxide, sodium phosphate, water glass, alkyl diphenyl base oxide stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate (DOWFAX 2A1) is respectively 10g/L, 60g/L, 15g/L, 0.1wt%;
B, the bolt workpiece after a process is immersed in mass concentration is completely in the hydrochloric acid soln of 10wt%, cleans 10min under room temperature in ultrasonic cleaner; Take out bolt workpiece, remove the hydrochloric acid soln of bolt workpiece surface with the cleaning of pure water;
C, the bolt workpiece after b process to be immersed in ethanol or acetone completely, in ultrasonic cleaner, to clean 25min under room temperature, take out for subsequent use;
The structure of (2) first protective films
Adopt magnetron sputtering technique to build the first protective film at bolt workpiece surface, concrete steps comprise:
A, to be greater than in vacuum indoor location purity 98% chromium target, make the angle of chromium target head and horizontal plane between 50 °; Bolt workpiece is placed on the work rest in vacuum chamber, vacuumizes, make the vacuum tightness in vacuum chamber be 1 × 10
-3pa; Employing rare gas element is working gas, cleans workpiece surface with ion source, and the air pressure range regulating ion source work is 2 × 10
-2pa, power is 120W, and scavenging period is 30min;
Regulating fender is relative with chromium target, and the power supply opening chromium target corresponding carries out pre-sputtering 5min;
B, employing helium are working gas, carry out sputtering sedimentation Cr film to bolt workpiece, and operating air pressure is 5Pa, and unit target sputtering power is 2W/cm
2, adopt at least one sputtering palladium to carry out sputtering sedimentation Cr film to bolt workpiece, sputtering time is 100s;
The mixed gas of c, employing nitrogen and helium is working gas, and the throughput ratio of nitrogen and helium is 4: 10, carries out sputtering sedimentation Cr (N) film to bolt workpiece, and operating air pressure is 5Pa, and unit target sputtering power is 1W/cm
2, adopt at least one sputtering palladium to carry out sputtering sedimentation Cr (N) film to bolt workpiece, sputtering time is 800s;
D, successively repeating step b, step c 10 times, make pure Cr layer and Cr (N) layer at the multi-layer film structure of the alternately laminated formation periodic arrangement of bolt workpiece surface;
Each step in this step (2) utilizes ion source to provide ion beam assisted depositing when carrying out simultaneously, and ion source operating voltage is 145V, and working current is 0.7A; Utilize additional power source hot donut, vacuum room temp is 50 DEG C; Utilize additional power source between work rest and vacuum chamber, apply the bias voltage of 0V;
(3) thermal treatment of bolt workpiece
Step (2) gained bolt workpiece is placed in retort furnace, and arranging heat-up rate is 5 DEG C/min, is incubated 1h, then furnace cooling after being warming up to 600 DEG C;
The structure of (4) second protective films
It is in the methanol solution of the methyl methacrylate of 3% that step (3) gained bolt workpiece is immersed in mass concentration, and Diisopropyl azodicarboxylate is added in this solution, the quality of this Diisopropyl azodicarboxylate is made to be 0.1% of methyl methacrylate quality, then at 50 DEG C, leave standstill 8h, take out and dry.
Embodiment 2:
The surface treatment method of the heavy antisepsis bolt of the present embodiment comprises the following steps:
(1) pre-treatment of bolt workpiece
A, bolt workpiece to be immersed in chemical alkali lye completely, after being heated to 75 DEG C, in ultrasonic cleaner, to clean 40min; Take out bolt workpiece, remove the chemical alkali lye of bolt workpiece surface with the cleaning of pure water;
Above-mentioned chemical alkali lye comprises sodium hydroxide, sodium phosphate, water glass, Witco 1298 Soft Acid and deionized water, and wherein, the concentration of sodium hydroxide, sodium phosphate, water glass, Witco 1298 Soft Acid is respectively 12g/L, 70g/L, 13g/L, 0.3wt%;
B, the bolt workpiece after a process is immersed in mass concentration is completely in the hydrochloric acid soln of 10wt%, cleans 5min under room temperature in ultrasonic cleaner; Take out bolt workpiece, remove the hydrochloric acid soln of bolt workpiece surface with the cleaning of pure water;
C, the bolt workpiece after b process to be immersed in ethanol or acetone completely, in ultrasonic cleaner, to clean 30min under room temperature, take out for subsequent use;
The structure of (2) first protective films
Adopt magnetron sputtering technique to build the first protective film at bolt workpiece surface, concrete steps comprise:
A, to be greater than in vacuum indoor location purity 98% chromium target, make the angle of chromium target head and horizontal plane between 45 °; Bolt workpiece is placed on the work rest in vacuum chamber, vacuumizes, make the vacuum tightness in vacuum chamber be 0.5 × 10
-3pa; Employing rare gas element is working gas, cleans workpiece surface with ion source, and the air pressure range regulating ion source work is 4 × 10
-2pa, power is 150W, and scavenging period is 10min;
Regulating fender is relative with chromium target, and the power supply opening chromium target corresponding carries out pre-sputtering 30min;
B, employing neon are working gas, carry out sputtering sedimentation Cr film to bolt workpiece, and operating air pressure is 0.1Pa, and unit target sputtering power is 1W/cm
2, adopt at least one sputtering palladium to carry out sputtering sedimentation Cr film to bolt workpiece, sputtering time is 1000s;
The mixed gas of c, employing nitrogen and neon is working gas, and the throughput ratio of nitrogen and neon is 5: 10, carries out sputtering sedimentation Cr (N) film to bolt workpiece, and operating air pressure is 2Pa, and unit target sputtering power is 2W/cm
2, adopt at least one sputtering palladium to carry out sputtering sedimentation Cr (N) film to bolt workpiece, sputtering time is 100s;
D, successively repeating step b, step c 15 times, make pure Cr layer and Cr (N) layer at the multi-layer film structure of the alternately laminated formation periodic arrangement of bolt workpiece surface;
Each step in this step (2) utilizes ion source to provide ion beam assisted depositing when carrying out simultaneously, and ion source operating voltage is 140V, and working current is 1.0A; Utilize additional power source hot donut, vacuum room temp is 100 DEG C; Utilize additional power source between work rest and vacuum chamber, apply the bias voltage of 400V;
(3) thermal treatment of bolt workpiece
Step (2) gained bolt workpiece is placed in retort furnace, and arranging heat-up rate is 6 DEG C/min, is incubated 2h, then furnace cooling after being warming up to 500 DEG C;
The structure of (4) second protective films
It is in the methanol solution of the methyl methacrylate of 4% that step (3) gained bolt workpiece is immersed in mass concentration, and Diisopropyl azodicarboxylate is added in this solution, the quality of this Diisopropyl azodicarboxylate is made to be 0.2% of methyl methacrylate quality, then at 55 DEG C, leave standstill 7h, take out and dry.
Embodiment 3:
The surface treatment method of the heavy antisepsis bolt of the present embodiment comprises the following steps:
(1) pre-treatment of bolt workpiece
A, bolt workpiece to be immersed in chemical alkali lye completely, after being heated to 80 DEG C, in ultrasonic cleaner, to clean 20min; Take out bolt workpiece, remove the chemical alkali lye of bolt workpiece surface with the cleaning of pure water;
Above-mentioned chemical alkali lye comprises sodium hydroxide, sodium phosphate, water glass, cocoyl isethionate (SCI-65) and deionized water, wherein, the concentration of sodium hydroxide, sodium phosphate, water glass, cocoyl isethionate (SCI-65) is respectively 15g/L, 65g/L, 10g/L, 0.5wt%;
B, the bolt workpiece after a process is immersed in mass concentration is completely in the hydrochloric acid soln of 5wt%, cleans 8min under room temperature in ultrasonic cleaner; Take out bolt workpiece, remove the hydrochloric acid soln of bolt workpiece surface with the cleaning of pure water;
C, the bolt workpiece after b process to be immersed in ethanol or acetone completely, in ultrasonic cleaner, to clean 20min under room temperature, take out for subsequent use;
The structure of (2) first protective films
Adopt magnetron sputtering technique to build the first protective film at bolt workpiece surface, concrete steps comprise:
A, to be greater than in vacuum indoor location purity 98% chromium target, make the angle of chromium target head and horizontal plane between 80 °; Bolt workpiece is placed on the work rest in vacuum chamber, vacuumizes, make the vacuum tightness in vacuum chamber be 0.8 × 10
-3pa; Employing rare gas element is working gas, cleans workpiece surface with ion source, and the air pressure range regulating ion source work is 6 × 10
-2pa, power is 100W, and scavenging period is 50min;
Regulating fender is relative with chromium target, and the power supply opening chromium target corresponding carries out pre-sputtering 25min;
B, employing argon gas are working gas, carry out sputtering sedimentation Cr film to bolt workpiece, and operating air pressure is 2Pa, and unit target sputtering power is 4W/cm
2, adopt at least one sputtering palladium to carry out sputtering sedimentation Cr film to bolt workpiece, sputtering time is 600s;
The mixed gas of c, employing nitrogen and argon gas is working gas, and the throughput ratio of nitrogen and argon gas is 5.5: 10, carries out sputtering sedimentation Cr (N) film to bolt workpiece, and operating air pressure is 0.1Pa, and unit target sputtering power is 3W/cm
2, adopt at least one sputtering palladium to carry out sputtering sedimentation Cr (N) film to bolt workpiece, sputtering time is 1000s;
D, successively repeating step b, step c 5 times, make pure Cr layer and Cr (N) layer at the multi-layer film structure of the alternately laminated formation periodic arrangement of bolt workpiece surface;
Each step in this step (2) utilizes ion source to provide ion beam assisted depositing when carrying out simultaneously, and ion source operating voltage is 150V, and working current is 1.2A; Utilize additional power source hot donut, vacuum room temp is 300 DEG C; Utilize additional power source between work rest and vacuum chamber, apply the bias voltage of 200V;
(3) thermal treatment of bolt workpiece
Step (2) gained bolt workpiece is placed in retort furnace, and arranging heat-up rate is 7 DEG C/min, is incubated 3h, then furnace cooling after being warming up to 550 DEG C;
The structure of (4) second protective films
It is in the methanol solution of the methyl methacrylate of 6% that step (3) gained bolt workpiece is immersed in mass concentration, and Diisopropyl azodicarboxylate is added in this solution, the quality of this Diisopropyl azodicarboxylate is made to be 0.3% of methyl methacrylate quality, then at 60 DEG C, leave standstill 6h, take out and dry.
Embodiment 4:
The surface treatment method of the heavy antisepsis bolt of the present embodiment comprises the following steps:
(1) pre-treatment of bolt workpiece
A, bolt workpiece to be immersed in chemical alkali lye completely, after being heated to 76 DEG C, in ultrasonic cleaner, to clean 50min; Take out bolt workpiece, remove the chemical alkali lye of bolt workpiece surface with the cleaning of pure water;
Above-mentioned chemical alkali lye comprises sodium hydroxide, sodium phosphate, water glass, α olefin sulfonate and deionized water, and wherein, the concentration of sodium hydroxide, sodium phosphate, water glass, α olefin sulfonate is respectively 13g/L, 64g/L, 12g/L, 0.2wt%;
B, the bolt workpiece after a process is immersed in mass concentration is completely in the hydrochloric acid soln of 15wt%, cleans 12min under room temperature in ultrasonic cleaner; Take out bolt workpiece, remove the hydrochloric acid soln of bolt workpiece surface with the cleaning of pure water:
C, the bolt workpiece after b process to be immersed in ethanol or acetone completely, in ultrasonic cleaner, to clean 27min under room temperature, take out for subsequent use;
The structure of (2) first protective films
Adopt magnetron sputtering technique to build the first protective film at bolt workpiece surface, concrete steps comprise:
A, to be greater than in vacuum indoor location purity 98% chromium target, make the angle of chromium target head and horizontal plane between 90 °; Bolt workpiece is placed on the work rest in vacuum chamber, vacuumizes, make the vacuum tightness in vacuum chamber be 1 × 10
-3pa; Employing rare gas element is working gas, cleans workpiece surface with ion source, and the air pressure range regulating ion source work is 7 × 10
-2pa, power is 130W, and scavenging period is 40min;
Regulating fender is relative with chromium target, and the power supply opening chromium target corresponding carries out pre-sputtering 20min;
B, employing Krypton are working gas, carry out sputtering sedimentation Cr film to bolt workpiece, and operating air pressure is 10Pa, and unit target sputtering power is 5W/cm
2, adopt at least one sputtering palladium to carry out sputtering sedimentation Cr film to bolt workpiece, sputtering time is 1500s;
The mixed gas of c, employing nitrogen and Krypton is working gas, and the throughput ratio of nitrogen and Krypton is 6: 10, carries out sputtering sedimentation Cr (N) film to bolt workpiece, and operating air pressure is 7Pa, and unit target sputtering power is 4W/cm
2, adopt at least one sputtering palladium to carry out sputtering sedimentation Cr (N) film to bolt workpiece, sputtering time is 600s;
D, successively repeating step b, step c 20 times, make pure Cr layer and Cr (N) layer at the multi-layer film structure of the alternately laminated formation periodic arrangement of bolt workpiece surface;
Each step in this step (2) utilizes ion source to provide ion beam assisted depositing when carrying out simultaneously, and ion source operating voltage is 155V, and working current is 0.8A; Utilize additional power source hot donut, vacuum room temp is 200 DEG C; Utilize additional power source between work rest and vacuum chamber, apply the bias voltage of 300V;
(3) thermal treatment of bolt workpiece
Step (2) gained bolt workpiece is placed in retort furnace, and arranging heat-up rate is 9 DEG C/min, is incubated 1.5h, then furnace cooling after being warming up to 520 DEG C;
The structure of (4) second protective films
It is in the methanol solution of the methyl methacrylate of 7% that step (3) gained bolt workpiece is immersed in mass concentration, and Diisopropyl azodicarboxylate is added in this solution, the quality of this Diisopropyl azodicarboxylate is made to be 0.25% of methyl methacrylate quality, then at 51 DEG C, leave standstill 7h, take out and dry.
Embodiment 5: the surface treatment method of the heavy antisepsis bolt of the present embodiment comprises the following steps:
(1) pre-treatment of bolt workpiece
A, bolt workpiece to be immersed in chemical alkali lye completely, after being heated to 78 DEG C, in ultrasonic cleaner, to clean 30min; Take out bolt workpiece, remove the chemical alkali lye of bolt workpiece surface with the cleaning of pure water;
Above-mentioned chemical alkali lye comprises sodium hydroxide, sodium phosphate, water glass, α-sodium olefin sulfonate and deionized water, and wherein, the concentration of sodium hydroxide, sodium phosphate, water glass, α-sodium olefin sulfonate is respectively 11g/L, 65g/L, 13g/L, 0.4wt%;
B, the bolt workpiece after a process is immersed in mass concentration is completely in the hydrochloric acid soln of 12wt%, cleans 12min under room temperature in ultrasonic cleaner; Take out bolt workpiece, remove the hydrochloric acid soln of bolt workpiece surface with the cleaning of pure water;
C, the bolt workpiece after b process to be immersed in ethanol or acetone completely, in ultrasonic cleaner, to clean 23min under room temperature, take out for subsequent use;
The structure of (2) first protective films
Adopt magnetron sputtering technique to build the first protective film at bolt workpiece surface, concrete steps comprise:
A, to be greater than in vacuum indoor location purity 98% chromium target, make the angle of chromium target head and horizontal plane between 60 °; Bolt workpiece is placed on the work rest in vacuum chamber, vacuumizes, make the vacuum tightness in vacuum chamber be 1 × 10
-3pa; Employing rare gas element is working gas, cleans workpiece surface with ion source, and the air pressure range regulating ion source work is 5 × 10
-2pa, power is 140W, and scavenging period is 20min;
Regulating fender is relative with chromium target, and the power supply opening chromium target corresponding carries out pre-sputtering 10min;
B, employing argon gas are working gas, carry out sputtering sedimentation Cr film to bolt workpiece, and operating air pressure is 7Pa, and unit target sputtering power is 3W/cm
2, adopt at least one sputtering palladium to carry out sputtering sedimentation Cr film to bolt workpiece, sputtering time is 800s;
The mixed gas of c, employing nitrogen and argon gas is working gas, and the throughput ratio of nitrogen and argon gas is 4.5: 10, carries out sputtering sedimentation Cr (N) film to bolt workpiece, and operating air pressure is 10Pa, and unit target sputtering power is 5W/cm
2, adopt at least one sputtering palladium to carry out sputtering sedimentation Cr (N) film to bolt workpiece, sputtering time is 1500s;
D, successively repeating step b, step c 25 times, make pure Cr layer and Cr (N) layer at the multi-layer film structure of the alternately laminated formation periodic arrangement of bolt workpiece surface;
Each step in this step (2) utilizes ion source to provide ion beam assisted depositing when carrying out simultaneously, and ion source operating voltage is 155V, and working current is 1.1A; Utilize additional power source hot donut, vacuum room temp is 150 DEG C; Utilize additional power source between work rest and vacuum chamber, apply the bias voltage of 250V;
(3) thermal treatment of bolt workpiece
Step (2) gained bolt workpiece is placed in retort furnace, and arranging heat-up rate is 10 DEG C/min, is incubated 2h, then furnace cooling after being warming up to 550 DEG C;
The structure of (4) second protective films
It is in the methanol solution of the methyl methacrylate of 3% that step (3) gained bolt workpiece is immersed in mass concentration, and Diisopropyl azodicarboxylate is added in this solution, the quality of this Diisopropyl azodicarboxylate is made to be 0.2% of methyl methacrylate quality, then at 57 DEG C, leave standstill 7h, take out and dry.
Carry out performance test to the bolt workpiece after process in the various embodiments described above, wherein, salt-fog test is pressed GB5938 neutral salt spray test (NSS) and is measured, and corrosion electric current density and corrosion potential are obtained by dynamic polarization curve.Concrete test result is as shown in table 1.
Table 1
Visible, the bolt workpiece after surface treatment method process of the present invention has excellent Corrosion Protection.
Alkyl diphenyl base oxide stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate (DOWFAX 2A1) in the present embodiment purchased from peak, Guangzhou one hundred along trade Co., Ltd, Witco 1298 Soft Acid is purchased from the southeast, Kunshan chemical materials company limited, cocoyl isethionate (SCI-65) is purchased from Guangzhou Hong Chang Chemical Co., Ltd., and α-sodium olefin sulfonate is prosperous and industrial chemicals company limited purchased from Yingkou City.
Claims (8)
1. a surface treatment method for heavy antisepsis bolt, is characterized in that comprising the following steps:
(1) pre-treatment of bolt workpiece
A, bolt workpiece to be immersed in chemical alkali lye completely, after being heated to 70 ~ 80 DEG C, in ultrasonic cleaner, to clean 20 ~ 60min; Take out bolt workpiece, remove the chemical alkali lye of bolt workpiece surface with the cleaning of pure water;
B, the bolt workpiece after a process is immersed in mass concentration is completely in the hydrochloric acid soln of 5 ~ 15wt%, cleans 5 ~ 15min under room temperature in ultrasonic cleaner; Take out bolt workpiece, remove the hydrochloric acid soln of bolt workpiece surface with the cleaning of pure water;
C, the bolt workpiece after b process is immersed in ethanol or acetone completely, in ultrasonic cleaner, cleans 20 ~ 30min under room temperature, take out for subsequent use;
The structure of (2) first protective films
Adopt magnetron sputtering technique to build the first protective film at bolt workpiece surface, concrete steps comprise:
A, to be greater than in vacuum indoor location purity 98% chromium target, make the angle of chromium target head and horizontal plane between 45 ° ~ 90 °; Bolt workpiece is placed on the work rest in vacuum chamber, vacuumizes, make the vacuum tightness in vacuum chamber be less than or equal to 1 × 10
-3pa; Employing rare gas element is working gas, cleans workpiece surface with ion source, and the air pressure range regulating ion source work is 2 × 10
-2~ 7 × 10
-2pa, power is 100 ~ 150W, and scavenging period is 10 ~ 50min;
B, employing rare gas element are working gas, carry out sputtering sedimentation Cr film to bolt workpiece, and operating air pressure is 0.1 ~ 10Pa, and unit target sputtering power is 1 ~ 5W/cm
2, adopt at least one sputtering palladium to carry out sputtering sedimentation Cr film to bolt workpiece, sputtering time is 100 ~ 1500s;
The mixed gas of c, employing nitrogen and rare gas element is working gas, and carry out sputtering sedimentation Cr (N) film to bolt workpiece, operating air pressure is 0.1 ~ 10Pa, and unit target sputtering power is 1 ~ 5W/cm
2, adopt at least one sputtering palladium to carry out sputtering sedimentation Cr (N) film to bolt workpiece, sputtering time is 100 ~ 1500s;
D, successively repeating step b, step c 5 ~ 25 times, make pure Cr layer and Cr (N) layer at the multi-layer film structure of the alternately laminated formation periodic arrangement of bolt workpiece surface;
(3) thermal treatment of bolt workpiece
Step (2) gained bolt workpiece is placed in retort furnace, and arranging heat-up rate is 5 ~ 10 DEG C/min, is incubated 1 ~ 3h, then furnace cooling after being warming up to 500 ~ 600 DEG C;
The structure of (4) second protective films
It is in the methanol solution of the methyl methacrylate of 3 ~ 8% that step (3) gained bolt workpiece is immersed in mass concentration, and Diisopropyl azodicarboxylate is added in this solution, the quality of this Diisopropyl azodicarboxylate is made to be 0.1 ~ 0.3% of methyl methacrylate quality, then at 50 ~ 60 DEG C, leave standstill 6 ~ 8h, take out and dry.
2. the surface treatment method of a kind of heavy antisepsis bolt according to claim 1, it is characterized in that: the chemical alkali lye described in step (1) comprises sodium hydroxide, sodium phosphate, water glass, sulphonic acids tensio-active agent and deionized water, the concentration of described sodium hydroxide, sodium phosphate, water glass, sulphonic acids tensio-active agent is respectively 10 ~ 15g/L, 60 ~ 70g/L, 10 ~ 15g/L, 0.1 ~ 0.5wt%.
3. the surface treatment method of a kind of heavy antisepsis bolt according to claim 2, is characterized in that: described sulphonic acids tensio-active agent is the one in sulphosuccinates, alkylbenzene sulfonate, alkylsulfonate, α olefin sulfonate.
4. the surface treatment method of a kind of heavy antisepsis bolt according to claim 1, is characterized in that: described rare gas element is the one in helium, neon, argon gas, Krypton.
5. the surface treatment method of a kind of heavy antisepsis bolt according to claim 1, it is characterized in that: after a step terminates in described step (2), before b step starts, regulating fender is relative with chromium target, and the power supply opening chromium target corresponding carries out pre-sputtering 5 ~ 30min.
6. the surface treatment method of a kind of heavy antisepsis bolt according to claim 1, is characterized in that: in described step (2) step c, the throughput ratio of nitrogen and rare gas element is 4 ~ 6: 10.
7. the surface treatment method of a kind of heavy antisepsis bolt according to claim 1, it is characterized in that: described step utilizes ion source to provide ion beam assisted depositing in (2), ion source operating voltage is 140 ~ 160V, and working current is 0.7 ~ 1.2A; Utilize additional power source hot donut, vacuum room temp is 50 ~ 300 DEG C; Utilize additional power source between work rest and vacuum chamber, apply the bias voltage of 0 ~ 400V.
8. the surface treatment method of a kind of heavy antisepsis bolt according to claim 1, is characterized in that: the first protective film thickness of step (2) gained bolt workpiece surface is 4 ~ 15 μm.
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