CN110158040B - Method for depositing magnesium on surface of polymer - Google Patents

Method for depositing magnesium on surface of polymer Download PDF

Info

Publication number
CN110158040B
CN110158040B CN201910549130.3A CN201910549130A CN110158040B CN 110158040 B CN110158040 B CN 110158040B CN 201910549130 A CN201910549130 A CN 201910549130A CN 110158040 B CN110158040 B CN 110158040B
Authority
CN
China
Prior art keywords
polymer
magnesium
layer
depositing
less
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910549130.3A
Other languages
Chinese (zh)
Other versions
CN110158040A (en
Inventor
廖斌
欧阳晓平
罗军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Normal University
Original Assignee
Beijing Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing Normal University filed Critical Beijing Normal University
Priority to CN201910549130.3A priority Critical patent/CN110158040B/en
Publication of CN110158040A publication Critical patent/CN110158040A/en
Application granted granted Critical
Publication of CN110158040B publication Critical patent/CN110158040B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/12—Organic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention relates to a method for depositing magnesium on the surface of a polymer, which comprises the following steps: cleaning the surface of the polymer; then co-depositing metal polymer and magnesium on the surface of the polymer by using an evaporation method and a cylindrical arc target; finally, the magnesium deposition is carried out by utilizing the cylindrical arc target. According to the method provided by the embodiment of the invention, the metal magnesium film layer is prepared by a method combining gas ion source cleaning, an evaporation method and cylindrical arc deposition, so that the bonding strength of the matrix and the metal magnesium layer is obviously improved. The method is simple, large in treatment area, easy to operate, low in cost and high in efficiency, and is very suitable for industrial mass production.

Description

Method for depositing magnesium on surface of polymer
Technical Field
The invention relates to a polymer surface modification technology, in particular to a method for depositing active metal on the surface of a polymer and a protection method.
Background
With the development of science and technology, magnesium as an active metal has wide application in the industries of medicine, electronics and the like. The magnesium film is mainly prepared and deposited on the surfaces of different substrates, but the bonding strength and subsequent protection of the magnesium film are a current difficult problem, and particularly the plating of the magnesium film on the surface of a polymer becomes a current key and difficult problem.
Disclosure of Invention
In order to solve the problems, the polymer and the magnesium metal need to be subjected to surface coupling, and treatment based on a cylindrical arc method and evaporation coupling is carried out, so that the film-substrate bonding strength of the polymer and the magnesium metal is improved, and the stability and the reliability of the polymer and the magnesium metal in different service environments are solved.
In view of this, the embodiment of the present invention provides a method for depositing magnesium on a polymer surface, including the following steps:
s110, alternately sputtering and cleaning the surface of the polymer at high pressure and low pressure;
s120, then, performing mixed deposition of metal magnesium and a polymer film on the surface by a coupled evaporation method and a cylindrical arc technology;
s130, depositing a metal magnesium film on the surface of the cylindrical arc target polymer;
s140, depositing an ultrathin polymer protective film layer on the surface based on an evaporation method;
preferably, the substrate is subjected to surface cleaning and polishing by using a gas ion source.
Further preferably, the ion source is a Hall source, and the cleaning mode is alternate high-low pressure cleaning; the first stage is 0-600V, the beam current is 2-5A, the treatment is 30min, and then 1200-1800V, the beam current is 0-1A, the treatment is 40 min.
Preferably, the polymer film is deposited by an evaporation method and simultaneously the cylindrical arc surface is matched for co-depositing magnesium, the polymer and the magnesium are co-deposited, the ratio of the evaporation deposition rate of the polymer to the deposition rate of the magnesium is not less than 2, the workpiece rotates during deposition, the speed is not less than 15r/min, the thickness of the co-deposited layer is not less than 50nm, and the resistivity of the co-deposited layer is not higher than 1 × 105Ω·m。
Preferably, when the magnesium is deposited, the arc starting current of the cylindrical arc is 0-90A, the effective width of the cylindrical arc is not less than 800mm, the surface temperature rise of the cathode is not more than 30 ℃, the surface temperature rise of the matrix is not more than 60 ℃ and the service life of the cathode is more than 100 h.
Preferably, in the process of depositing the ultrathin protective film layer by an evaporation method, the surface temperature of the substrate does not exceed 50 ℃, the deposition rate is less than 10nm/min, and the thickness does not exceed 100 nm; the thickness of the surface oxidation layer of the inner magnesium layer is not more than 10nm under the environment that the temperature is 80 ℃ and the humidity is 80 percent under the protection of the ultrathin polymer film layer.
Compared with the prior art, the embodiment of the invention has the following advantages:
(1) the gas ion source technology and the high-low pressure cleaning process can be utilized to conveniently form a layer of high surface energy combination surface on the surface of the matrix, and the surface roughness and the like can be conveniently regulated and controlled through ion energy and beam current; the interface can be well jointed with a subsequent film layer after regulation and control, and compared with other surface cleaning technologies, the film layer prepared by the technology and the process disclosed by the invention has better bonding force with a substrate.
(2) Compared with magnetron sputtering and magnetic filtration deposition technologies, the cylindrical arc deposition of the magnesium film is high in speed and small in particle size; meanwhile, the cylindrical arc can conveniently control the temperature of the cathode due to the large surface area.
(3) Compared with the traditional method for solving the film-substrate bonding strength, the method disclosed by the invention has the advantages that the deposition of the high-bonding-strength metal film layer can be conveniently realized by depositing the magnesium-doped polymer transition film layer based on the evaporation and cylindrical arc technologies, so that the film-substrate bonding strength is greatly improved; meanwhile, the included angle between the evaporation device and the cylindrical arc target is 30-60 degrees, a transition layer with the polymer magnesium doping range of 5-15 percent can be obtained within the angle range, and the polymer can be strongly bonded with the matrix while keeping good characteristics within the range.
(4) Compared with the traditional active metal protective film layer technology, the thickness of the ultrathin film layer is not more than 100nm, and the ultrathin film layer is essentially different from the traditional technology in the covering and wrapping thickness of more than 1 mu m; the film layer prepared by the traditional method has high surface roughness, and the thickness of the film layer to be protected is thicker, but the surface roughness of the film layer prepared by the cylindrical arc deposition method is lower, and the thinner film layer can realize covering.
(5) Compared with the single-source gas target cleaning in the prior art, the invention adopts two groups of gas ion source targets for cleaning, and the included angle between the two gas ion sources is not less than 80 degrees, so that the stepped and alternate cleaning effect is greatly increased under the angle, the nano-scale roughness of the surface of the membrane is enhanced, and the bonding strength with a subsequent membrane is increased.
Drawings
The accompanying drawings, which are included to provide a further understanding of embodiments of the invention, are incorporated in and constitute a part of this specification.
FIG. 1 is a schematic flow chart of a method for depositing magnesium on a polymer surface according to an embodiment of the present invention;
FIG. 2 is a diagram of a cylindrical arc structure in accordance with an embodiment of the present invention;
FIG. 3 is a diagram of an apparatus for depositing magnesium on a polymer surface according to an embodiment of the present invention;
FIG. 4 is a schematic diagram of a polymer surface deposited magnesium layer according to an embodiment of the present invention;
FIG. 5 is a graph showing surface topography and hydrophilicity after ion source treatment according to an embodiment of the present invention;
FIG. 6 shows the bonding strength of magnesium metal deposited on a polymer surface and the surface energy of the polymer after alternate cleaning, which are provided in examples 1-5 of the present invention.
Description of reference numerals:
101-cylindrical arc Mg cathode
102-anode
103-trigger electrode
201-gas ion Source
202-Evaporation apparatus
203-cylindrical arc target
204 sample stage
205-cylindrical arc target
206-Evaporation device
207-gas ion Source
301 — a polymer matrix;
302-a magnesium doped polymer transition layer;
303-a layer of metallic magnesium;
304-an ultra-thin polymer protective layer;
Detailed Description
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
In addition, it should be noted that the materials and test methods used in the experiments of the present invention are generally described in this section. Although many materials and methods of operation are known in the art for the purpose of carrying out the invention, the invention is nevertheless described herein in as detail as possible. It will be apparent to those skilled in the art that the materials and methods of operation used in the present invention are well within the skill of the art, provided that they are not specifically illustrated.
Fig. 1 is a schematic flow chart of a method for preparing a heat dissipation coating according to an embodiment of the present invention, where as shown in fig. 1, the method includes the following steps:
s110, alternately sputtering and cleaning the surface of the polymer at high pressure and low pressure;
the ion source is a Hall source, and the cleaning mode is alternate high-pressure and low-pressure cleaning; the first stage is 0-600V, the beam current is 2-5A, the treatment is 30min, and then 1200-1800V, the beam current is 0-1A, the treatment is 40 min.
Compared with the traditional cleaning technology, the cleaning efficiency of the polymer substrate can be greatly improved by alternately cleaning the polymer substrate with high and low voltage beams, the roughness change of the surface of the cleaned polymer substrate can be conveniently controlled by alternately cleaning, the roughness of the surface of the treated polymer is increased by 10-30nm, and the subsequent bonding strength with the film layer is greatly improved.
S120, then, performing mixed deposition of metal magnesium and a polymer film on the surface by a coupled evaporation method and a cylindrical arc technology;
depositing polymer film by evaporation method while co-depositing magnesium on the surface of cylindrical arc, the polymer and magnesium are co-deposited, the ratio of polymer evaporation deposition rate to magnesium deposition rate is not less than 2, the workpiece rotates automatically during deposition, the speed is not less than 15r/min, the thickness of co-deposited layer is not less than 50nm, and the resistivity is not higher than 1 × 105Ω·m。
The magnesium-doped polymer transition film layer deposited based on the evaporation and cylindrical arc technology can conveniently realize the deposition of the metal film layer with high bonding strength, thereby greatly improving the bonding strength of the film and the substrate; meanwhile, the included angle between the evaporation device and the cylindrical arc target is 30-60 degrees, a transition layer with the polymer magnesium doping range of 5-15 percent can be obtained within the angle range, and the polymer can be strongly bonded with the matrix while keeping good characteristics within the range.
S130, depositing a metal magnesium film on the surface of the cylindrical arc target polymer;
when depositing magnesium, the arc starting current of the cylindrical arc is 0-90A, and the arc starting vacuum degree is 3 × 10-3Pa, the effective width of the cylindrical arc is not less than 800mm, the surface temperature rise of the cathode is not more than 30 ℃ when the cathode works, the surface temperature rise of the substrate is not more than 60 ℃, and the service life of the cathode is more than 100 h.
Compared to conventional arc deposition techniques: 1) the overall length of the deposited cylindrical arc is 1000mm, and the effective processing width is more than 800 mm; 2) because of the problem of low arcing current, the surface temperature of the cathode can be well controlled, which is not possessed by the traditional round target/column target arc; 3) the traditional circular/cylindrical arc target arcing works under auxiliary gas, and particularly the arcing vacuum degree of the cylindrical arc target is 10-2Within-10 Pa, none at 10-3A process and equipment for stabilizing arc under Pa vacuum.
S140, depositing an ultrathin polymer protective film layer on the surface based on an evaporation method;
in the process of depositing the ultrathin protective film layer by an evaporation method, the surface temperature of a substrate does not exceed 50 ℃, the deposition rate is less than 10nm/min, and the thickness does not exceed 100 nm; the thickness of the surface oxidation layer of the inner magnesium layer is not more than 10nm under the environment that the temperature is 80 ℃ and the humidity is 80 percent under the protection of the ultrathin polymer film layer.
Compared with the traditional active metal protective film layer technology, the thickness of the ultrathin film layer is not more than 100nm, and the ultrathin film layer is essentially different from the traditional technology in the covering and wrapping thickness of more than 1 mu m; the film layer prepared by the traditional method has high surface roughness, and the thickness of the film layer to be protected is thicker, but the surface roughness of the film layer prepared by the cylindrical arc deposition method is lower, and the thinner film layer can realize covering.
In an example, the surface is cleaned using a gas ion source method, in which process the gas ion source apparatus is preferably an anode layer ion source apparatus. The cleaning element may be, in principle, an inert gas element, and is preferably an element such as Ar or Kr. In one possible embodiment, the beam intensity during cleaning is 0-2A, preferably 1-2A. The gas ion source equipment, the electric arc equipment and the outgoing beam of the magnetic filtering deposition are all large in area, and the beam diameter can reach 800mm, so that the large-batch treatment of the matrix can be realized, the cost is low, and the efficiency is high.
The preparation method of the heat dissipation coating provided by the embodiment mainly utilizes a gas ion source, a cylindrical arc deposition technology and an evaporation technology to perform deposition treatment, so as to form a metal magnesium film on the surface of a substrate. In addition, before deposition and coating, a gas ion source method is utilized to form a 'fresh' atomic layer on the subsurface of the base material, so that the bonding force between a subsequent deposited film layer and the substrate is further increased, and meanwhile, the bonding strength between the base body and a subsequent metal layer is also greatly improved through operations such as codeposition of a doped metal polymer transition layer and the like.
The technical scheme provided by the invention is utilized to better embody the performance such as better bonding force, the experimental parameters are simply regulated and controlled, and then the bonding strength and the surface energy are compared. .
Example one
S110, alternately sputtering and cleaning the surface of the polymer at high pressure and low pressure;
the ion source is an anode layer ion source, the power is 0-3KW, and the beam current is 0-2A; the first stage is 200V, the beam current is 5A, the treatment is carried out for 30min, and then 1800V, the beam current is 0.6A, the treatment is carried out for 40 min;
s120, then, performing mixed deposition of metal magnesium and a polymer film on the surface by a coupled evaporation method and a cylindrical arc technology, wherein the cylindrical target magnesium has the arcing current of 70A, and the arcing vacuum degree is 3 × 10-3Pa, co-depositing the polymer and magnesium at the speed of 18r/min, wherein the ratio of the evaporation deposition rate of the polymer to the deposition rate of the magnesium is not less than 2, and the thickness of the co-deposited layer is 50 nm;
s130, depositing a metal magnesium film on the surface of the cylindrical arc target polymer, wherein the arcing vacuum degree is 1 × 10-3-3×10-3Pa, the arcing current is 0-90A, and the thickness of the magnesium layer is 0-1 μm;
s140, depositing an ultrathin polymer protective film layer on the surface based on an evaporation method; the surface temperature during deposition is not more than 50 ℃, the deposition rate is less than 10nm/min, and the thickness is not more than 100 nm.
Example two
S110, alternately sputtering and cleaning the surface of the polymer at high pressure and low pressure;
the ion source is an anode layer ion source, the power is 0-3KW, and the beam current is 0-2A; in the first stage, 300V is carried out, the beam current is 4A, the treatment is carried out for 30min, and then 1700V is carried out, the beam current is 0.7A, and the treatment is carried out for 40 min;
s120, then, the metal magnesium and the polymer film are mixed and deposited on the surface by the coupling evaporation method and the cylindrical arc technology, the cylindrical target magnesium arcing current is 80A, the arcing vacuum degree is 3 × 10-3Pa, co-depositing the polymer and magnesium at a speed of 20r/min, wherein the ratio of the evaporation deposition rate of the polymer to the deposition rate of the magnesium is not less than 2, and the thickness of the co-deposited layer is 60 nm;
s130, depositing a metal magnesium film on the surface of the cylindrical arc target polymer, wherein the arcing vacuum degree is 1 × 10-3-3×10-3Pa, the arcing current is 0-90A, and the thickness of the magnesium layer is 0-1 μm;
s140, depositing an ultrathin polymer protective film layer on the surface based on an evaporation method; the surface temperature during deposition is not more than 50 ℃, the deposition rate is less than 10nm/min, and the thickness is not more than 100 nm.
EXAMPLE III
S110, alternately sputtering and cleaning the surface of the polymer at high pressure and low pressure;
the ion source is an anode layer ion source, the power is 0-3KW, and the beam current is 0-2A; in the first stage, 400V is carried out, the beam current is 3A, the treatment is carried out for 30min, and then 1600V is carried out, the beam current is 0.8A, and the treatment is carried out for 40 min;
s120, then, the metal magnesium and the polymer film are mixed and deposited on the surface by the coupling evaporation method and the cylindrical arc technology, the cylindrical target magnesium arcing current is 80A, the arcing vacuum degree is 3 × 10-3Pa, co-depositing the polymer and magnesium at the speed of 20r/min, wherein the ratio of the evaporation deposition rate of the polymer to the deposition rate of the magnesium is not less than 2, and the thickness of the co-deposition layer is 80 nm;
s130, depositing a metal magnesium film on the surface of the cylindrical arc target polymer, wherein the arcing vacuum degree is 1 × 10-3-3×10-3Pa, the arcing current is 0-90A, and the thickness of the magnesium layer is 0-1 μm;
s140, depositing an ultrathin polymer protective film layer on the surface based on an evaporation method; the surface temperature during deposition is not more than 50 ℃, the deposition rate is less than 10nm/min, and the thickness is not more than 100 nm.
Example four
S110, alternately sputtering and cleaning the surface of the polymer at high pressure and low pressure;
the ion source is an anode layer ion source, the power is 0-3KW, and the beam current is 0-2A; in the first stage, 500V is carried out, the beam current is 2A, the treatment is carried out for 30min, and then 1400V is carried out, the beam current is 0.9A, and the treatment is carried out for 40 min;
s120, then, the metal magnesium and the polymer film are mixed and deposited on the surface by the coupling evaporation method and the cylindrical arc technology, the cylindrical target magnesium arcing current is 80A, the arcing vacuum degree is 3 × 10-3Pa, co-depositing the polymer and magnesium at a speed of 22r/min, wherein the ratio of the evaporation deposition rate of the polymer to the deposition rate of the magnesium is not less than 2, and the thickness of the co-deposited layer is 100 nm;
s130, depositing a metal magnesium film on the surface of the cylindrical arc target polymer, wherein the arcing vacuum degree is 1 × 10-3-3×10-3Pa, the arcing current is 0-90A, and the thickness of the magnesium layer is 0-1 μm;
s140, depositing an ultrathin polymer protective film layer on the surface based on an evaporation method; the surface temperature during deposition is not more than 50 ℃, the deposition rate is less than 10nm/min, and the thickness is not more than 100 nm.
EXAMPLE five
S110, alternately sputtering and cleaning the surface of the polymer at high pressure and low pressure;
the ion source is an anode layer ion source, the power is 0-3KW, and the beam current is 0-2A; in the first stage, 600V is carried out, the beam current is 2A, the treatment is carried out for 30min, and then 1200V is carried out, the beam current is 1A, and the treatment is carried out for 40 min;
s120, then, performing mixed deposition of metal magnesium and a polymer film on the surface by a coupled evaporation method and a cylindrical arc technology, wherein the cylindrical target magnesium has an arc starting current of 90A and an arc starting vacuum degree of 3 × 10-3Pa, co-depositing the polymer and magnesium at a speed of 25r/min, wherein the ratio of the evaporation deposition rate of the polymer to the deposition rate of the magnesium is not less than 2, and the thickness of the co-deposition layer is 150 nm;
s130, depositing a metal magnesium film on the surface of the cylindrical arc target polymer, wherein the arcing vacuum degree is 1 × 10-3-3×10-3Pa, the arcing current is 0-90A, and the thickness of the magnesium layer is 0-1 μm;
s140, depositing an ultrathin polymer protective film layer on the surface based on an evaporation method; the surface temperature during deposition is not more than 50 ℃, the deposition rate is less than 10nm/min, and the thickness is not more than 100 nm.
FIG. 1 is a schematic diagram of a method for depositing magnesium by using a polymer. FIG. 2 is a schematic diagram of a cylindrical arc target structure, which is composed of a trigger electrode, an anode and a magnesium cathode. FIG. 3 is a structural diagram of a method and equipment for depositing magnesium on the surface of a polymer, wherein the equipment consists of two sets of gas ion sources, two sets of cylindrical arc targets and two sets of evaporation devices, the included angle between each evaporation device and the cylindrical arc target is 30-60 degrees, and the included angle between each two gas ion sources is not less than 80 degrees. FIG. 4 shows an exemplary coating structure, wherein the magnesium coating structure comprises a polymer substrate, a magnesium metal doped layer, a magnesium metal layer, and a polymer protective layer. FIG. 5 is a surface topography and hydrophilicity test chart of an embodiment, which shows that the surface energy of the polymer is obviously fluctuated by the alternate high and low sputtering cleaning, and the hydrophilic angle is reduced, thereby showing that the surface energy of the polymer is increased. FIG. 6 is a graph showing the results of the surface adhesion test after magnesium plating and the surface energy test after alternate cleaning in five examples, and it is apparent from the graph that cleaning is performedThe surface energy is greatly increased to 110J/m2. The bonding strength of the magnesium and the polymer matrix is more than 0.7Kg/cm, and the highest bonding strength can be 1.1Kg/cm, which is far more than 0.6Kg/cm of the industrial application standard. Meanwhile, the method is simple, easy to operate, low in cost, high in efficiency and very suitable for industrial mass production.
It is to be noted that although the present invention has been described to a certain extent, it is apparent that various suitable changes in conditions may be made without departing from the spirit and scope of the present invention. It is to be understood that the invention is not limited to the described embodiments, but is to be accorded the scope consistent with the claims, including equivalents of each element described.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (7)

1. A method for depositing magnesium on the surface of a polymer is characterized by comprising the following steps:
s110, alternately sputtering and cleaning the surface of the polymer at high pressure and low pressure; the ion source is an anode layer ion source, the power is 0-3KW, and the beam current is 0-5A; the first stage is 0-600V, the beam current is 2-5A, the treatment is carried out for 30min, and then 1200V and 1800V, the beam current is 0-1A, the treatment is carried out for 40 min;
s120, then, the metal magnesium and the polymer film are mixed and deposited on the surface by the coupling evaporation method and the cylindrical target technology, the arc starting current of the cylindrical magnesium target is 0-90A, the arc starting vacuum degree is 1 × 10-3-3×10-3Pa, co-depositing the polymer and magnesium, wherein the ratio of the evaporation deposition rate of the polymer to the deposition rate of the magnesium is not less than 2;
s130, then depositing a metal magnesium film on the surface of the polymer based on a cylindrical magnesium target, wherein the arcing current is 0-90A, and the arcing vacuum degree is 1 × 10-3-3×10-3Pa, the thickness of the magnesium layer is 0-1 μm;
and S140, depositing an ultrathin polymer protective film layer on the surface based on an evaporation method, wherein the thickness of the ultrathin polymer protective film layer is 50-100 nm.
2. The method of claim 1, wherein the anode layer ion source treatment width dimension is not less than 800mm, the temperature rise of the polymer during treatment is not more than 50 ℃, and the surface roughness of the polymer increases by 10 to 30nm after treatment.
3. The method of claim 1, wherein the cylindrical target has an effective width of no less than 800mm, a cathode surface temperature rise of no greater than 30 ℃, a substrate surface temperature rise of no greater than 60 ℃, and a cathode lifetime of greater than 100 hours during operation.
4. The method of claim 1, wherein the anode layer ion source is treated to co-deposit magnesium metal and polymer, the workpiece rotates during deposition at a speed of not less than 15r/min, the thickness of the co-deposited layer is not less than 50nm, the doping concentration of magnesium is 5-15%, and the resistivity is not higher than 1 × 105Ω·m。
5. The method of claim 1, wherein the temperature of the substrate surface during the deposition of the ultra-thin protective film layer does not exceed 50 ℃ and the deposition rate is less than 10 nm/min.
6. The method of claim 1, wherein the thickness of the surface oxide layer of the magnesium in the inner layer is not more than 10nm under the environment of 80 ℃ and 80% humidity when the film-coated sample is protected by the ultra-thin polymer film layer.
7. The method of claim 1, wherein the deposition apparatus is provided with two sets of anode layer ion sources, two sets of evaporation devices and two sets of cylindrical arc targets, the evaporation devices and the cylindrical arc targets are at an angle of 30 ° to 60 °, and the gas ion sources are at an angle of not less than 80 °.
CN201910549130.3A 2019-06-24 2019-06-24 Method for depositing magnesium on surface of polymer Active CN110158040B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910549130.3A CN110158040B (en) 2019-06-24 2019-06-24 Method for depositing magnesium on surface of polymer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910549130.3A CN110158040B (en) 2019-06-24 2019-06-24 Method for depositing magnesium on surface of polymer

Publications (2)

Publication Number Publication Date
CN110158040A CN110158040A (en) 2019-08-23
CN110158040B true CN110158040B (en) 2020-09-01

Family

ID=67625643

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910549130.3A Active CN110158040B (en) 2019-06-24 2019-06-24 Method for depositing magnesium on surface of polymer

Country Status (1)

Country Link
CN (1) CN110158040B (en)

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109295426B (en) * 2018-12-10 2020-05-19 北京师范大学 Ultra-wide and uniform magnetic filtering system, cylindrical arc target and vacuum equipment

Also Published As

Publication number Publication date
CN110158040A (en) 2019-08-23

Similar Documents

Publication Publication Date Title
JPH01294867A (en) Formation of coating film of carbon or consisting essentially of carbon
US4502931A (en) Process for the production of ion exchange membranes with coating for electrolysis
JP7035068B2 (en) Manufacturing method of bipolar plate for fuel cell
CN109560289B (en) Metal bipolar plate, preparation method thereof and fuel cell
JP2012506130A5 (en)
CN111763945A (en) Razor blade with multilayer reinforced coating and preparation method thereof
CN113088911A (en) Metal-doped molybdenum disulfide ultra-smooth film and preparation method thereof
CN110158040B (en) Method for depositing magnesium on surface of polymer
CN102534514A (en) Method for plating films of multi-arc ion plating
JP2016132807A (en) Sputtering apparatus and method for manufacturing thin film
KR101888557B1 (en) ta-C composite coating layer, apparatus for manufacturing ta-C composite coating layer and method for manufacturing using the same
TWI490354B (en) Housing and method for making the same
CN116855888A (en) Flexible high-entropy alloy coating and preparation method and application thereof
CN111041430A (en) Production process of high-temperature-resistant diamond-like carbon film layer
JPS61295371A (en) Production of aluminum material having aluminum nitride layer
US20230411104A1 (en) Method of forming field emission cathodes by co-electrodeposition
TWI490358B (en) Housing and method for making the same
CN110783595B (en) Metal bipolar plate, preparation method thereof and fuel cell
JP4510358B2 (en) Electrostatic chuck and manufacturing method thereof
JP2010116303A (en) Substrate for growing carbon nanotube, transistor, and method for manufacturing substrate for growing carbon nanotube
TWI486476B (en) Housing and method for making the same
US20230411103A1 (en) Methods for forming carbon nanotube/metal composite films and field emission cathodes therefrom
JP5261844B2 (en) Protective substrate and method of manufacturing protective substrate
RU2813858C1 (en) Method of increasing efficiency of multi-tip electron field emission cathodes
WO2022070094A1 (en) Methods of forming a field emission cathode

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant