CN113278931A - Method for thickening magnetron sputtering coating on surface of composite material - Google Patents
Method for thickening magnetron sputtering coating on surface of composite material Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 114
- 239000011248 coating agent Substances 0.000 title claims abstract description 104
- 239000002131 composite material Substances 0.000 title claims abstract description 103
- 238000001755 magnetron sputter deposition Methods 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 36
- 230000008719 thickening Effects 0.000 title claims abstract description 24
- 239000013077 target material Substances 0.000 claims abstract description 65
- 239000003822 epoxy resin Substances 0.000 claims abstract description 49
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 42
- 238000007747 plating Methods 0.000 claims abstract description 29
- 238000004140 cleaning Methods 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000007781 pre-processing Methods 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 230000009477 glass transition Effects 0.000 claims abstract description 10
- 229910052786 argon Inorganic materials 0.000 claims abstract description 8
- 238000001291 vacuum drying Methods 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 8
- 238000005336 cracking Methods 0.000 abstract description 15
- 239000010410 layer Substances 0.000 description 35
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- 210000002381 plasma Anatomy 0.000 description 21
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- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000001133 acceleration Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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- 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
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- 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
- C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
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Abstract
The invention discloses a method for thickening a magnetron sputtering coating on the surface of a composite material, which comprises the following steps: 1, pre-cleaning, namely cleaning and drying the surface of the composite material by adopting an ethanol reagent; 2, preprocessing, namely preprocessing the aluminum target material and the preprocessed composite material by glow discharge generated by plasma; 3, magnetron sputtering coating, namely performing magnetron sputtering coating on the pretreated composite material by adopting an aluminum target material, wherein the current intensity is 3.8-4.2A, and the vacuum pressure is lower than 10 when the magnetron sputtering coating starts‑3Pa, argon protection, 5.5-6.5 hours; the composite material is an epoxy resin-based material. The method for preparing the pure aluminum coating on the surface of the epoxy resin-based composite material has the advantages that the thickness of the pure aluminum coating exceeds 20 mu m, the coating is qualified in appearance, the bad phenomena of bulging, cracking, falling and the like are avoided, and the layer-base bonding strength is more than 0.4 MPa. The performance of the film layer after plating is good, and the working temperature is lower than the glass transition temperature of the epoxy resin material.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a method for thickening a magnetron sputtering coating on the surface of a composite material.
Background
The epoxy resin-based composite material has high specific strength and specific modulus and excellent mechanical property, but also has the defects of poor resistance to special medium corrosion, existence of gaps and poor heat conduction. In actual work, the surface of the material needs to be treated to ensure that the corrosion resistance, the porosity and the thermal conductivity meet the requirements of the actual work, so that a set of suitable methods needs to be established. The epoxy resin-based composite material belongs to a porous material, and metal ions in electroplating or chemical plating liquid are attached to pores and corrode the composite material, so that the mechanical property is reduced to cause failure, and the service life and reliability of the material are influenced. The magnetron sputtering coating technology is applied at the early stage, but the thickness of the surface treatment layer is low, and the roughness Rt value of the composite material matrix is high, so that the phenomenon of discontinuous coating is possibly caused, and the coating has certain influence on air tightness. When a thicker magnetron sputtering film layer is plated, the adverse phenomena of cracking, bulging and the like of the plating layer often occur.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for thickening a magnetron sputtering coating on the surface of a composite material, wherein the performance of the coating after plating is good, and the working temperature is lower than the glass transition temperature of an epoxy resin material.
The invention is realized by the following technical scheme:
the method for thickening the magnetron sputtering coating on the surface of the composite material comprises the following steps:
step 1, pre-cleaning, namely cleaning the surface of the composite material by using an ethanol reagent, and then drying the cleaned composite material to obtain the pre-cleaned composite material; the pre-cleaning aims to remove impurity components on the surface of the matrix, ensure the stability of a film forming interface and avoid the phenomena of bulging and cracking of a film layer caused by unclean composite material matrix.
Step 2, preprocessing, namely preprocessing the target material and the preprocessed composite material by glow discharge generated by plasma to obtain a preprocessed target material and a preprocessed composite material; the glow treatment aims at preheating the target material and the substrate material, is beneficial to increasing the layer-substrate bonding force and cleaning the substrate finally.
Step 3, performing magnetron sputtering coating, namely performing magnetron sputtering coating on the pretreated composite material by adopting the pretreated target material, wherein the magnetron sputtering coating process parameters are as follows: the current intensity is 3.8-4.2A, and the vacuum pressure is lower than 10 when the magnetron sputtering coating starts-3Pa, argon protection, and magnetron sputtering coating time of 5.5-6.5 hours;
the composite material is an epoxy resin-based material;
the target material is aluminum.
In the above technical solution, the ethanol reagent in step 1 is analytically pure.
In the technical scheme, the drying process in the step 1 is vacuum drying, the vacuum degree is 1-20 Pa, and the vacuum drying time is 2-3 hours.
In the above technical solution, the drying process in the step 1 is vacuum drying, and the temperature of the vacuum drying is lower than the glass transition temperature of the composite material.
In the technical scheme, in the step 2, the current intensity in the glow discharge process is 0.8-1.2A, and the duration is 3-10 minutes.
In the above technical scheme, in step 3, the magnetic field intensity control parameters of the equipment adopted for magnetron sputtering coating are as follows: magnetic performance parameters of the single magnetic stripe: remanence (Br) 1.18-1.22T, coercive force (Hcb) > 876KA/m, maximum magnetic energy product (BH) 263-287 KJ/m3(20 ℃ C.); the working temperature is less than or equal to 80 ℃.
In the technical scheme, in the step 3, the target material in the equipment adopted by the magnetron sputtering coating is a cylindrical target material, the diameter of the target material is 45-55 mm, the length of the target material is 600-800 mm, the effective length range of the target material is 550-650 mm, and the number of magnetic stripe channels in the target material is 4.
In the technical scheme, in the step 3, the distance between the target and the composite material in the equipment adopted by the magnetron sputtering coating is 40-50 mm.
In the above technical solution, in the step 3, the length of the composite material to be plated does not exceed the effective range of the length of the target.
The invention has the advantages and beneficial effects that:
when thicker metal coating is deposited, electroplating or chemical plating is mostly adopted, and cases and technologies for developing thicker coatings by adopting a direct current magnetron sputtering technology are rare. The significance of performing magnetron sputtering on the surface of an epoxy resin-based composite material is that the composite material belongs to a porous material, the composite material is required to be soaked in plating solution for electroplating or chemical plating, the plating solution and metal ions are easy to attach to pores, and the inside of the composite material is corroded after a certain time, so that the mechanical property of the composite material is reduced, the composite material is invalid, the service life and the reliability of the material are influenced, and therefore, an environment-friendly technology is required to be adopted.
The patent relates to a process capable of plating a thicker magnetron sputtering film layer, in particular to a process capable of using a magnetron sputtering method to prepare a qualified pure aluminum plating layer on the surface of a composite material mainly based on an epoxy resin base by selecting proper current intensity, plating time and target and substrate distance in step 3, ensuring that the appearance of the plating layer is qualified, and avoiding the cracking phenomenon caused by the reduction of binding force and the increase of internal stress due to the thickening of the film layer.
The effect of the invention is that the thickness of the pure aluminum coating on the surface of the composite material mainly based on the epoxy resin matrix is more than 20 μm, the coating is qualified in appearance, the bad phenomena of bulging, cracking, falling and the like are avoided, and the layer-base bonding strength is more than 0.4 MPa. The performance of the film layer after plating is good, and the working temperature is lower than the glass transition temperature of the epoxy resin material.
Drawings
FIG. 1 is a cross-sectional view of a plated layer obtained by metallographic sampling an epoxy resin matrix composite material in a radial direction in a final product according to example 1 of the present invention.
FIG. 2 is an XRD spectrum of an Al coating layer prepared by the invention;
wherein a is an XRD (X-ray diffraction) spectrum of the Al coating layer prepared in the example 1; b is the XRD spectrum of the Al coating layer prepared in example 3.
For a person skilled in the art, other relevant figures can be obtained from the above figures without inventive effort.
Detailed Description
In order to make the technical solution of the present invention better understood, the technical solution of the present invention is further described below with reference to specific examples.
In the following examples, the plating thickness was measured by cutting the plating section to prepare a metallographic specimen according to GB/T4677.6-84 test methods for the thickness of metal and oxide coatings, and the metallographic specimen was measured by an Axiotech-100 metallographic microscope.
The method for testing the bonding strength of the plating layer is a direct stretching method, after the plating layer on the surface of the sample is bonded and solidified with the bonding rod, the sample is stretched in a SUNS-CMT5205 mechanical tensile testing machine, the plating layer and the substrate are peeled off along the vertical direction, and the bonding strength is calculated according to the peeling force value and the bonding area.
The XRD test equipment is a D/MAX powder X-ray diffractometer, and the test parameters are as follows: cu (40kv \200mA), a scanning angle 2 theta of 5-90 degrees and a scanning angle of 4 DEG/min.
Example 1
A method for thickening a magnetron sputtering coating on the surface of a composite material comprises the following steps:
step 1, pre-cleaning, wherein the length of a composite material to be plated is 500mm, cleaning the surface of an epoxy resin-based material for 3 times by using an ethanol analysis reagent, and then drying the cleaned composite material to obtain the pre-cleaned epoxy resin-based material; the pre-cleaning aims to remove impurity components on the surface of the matrix, ensure the stability of a film forming interface and avoid the phenomena of bulging and cracking of a film layer caused by unclean composite material matrix. The drying process is vacuum drying, the vacuum degree is 12Pa, and the vacuum drying time is 2.5 hours; the temperature of vacuum drying is lower than the glass transition temperature of the epoxy resin;
step 2, preprocessing, namely preprocessing the aluminum target material and the epoxy resin base material after being preprocessed through glow discharge (current intensity is 1A, duration is 5min) generated by plasma, so as to obtain the preprocessed target material and the preprocessed epoxy resin base material; the glow treatment aims at preheating the target material and the substrate material, is beneficial to increasing the layer-substrate bonding force and cleaning the substrate finally.
Step 3, performing magnetron sputtering coating, namely performing magnetron sputtering coating on the pretreated epoxy resin base material by adopting the pretreated target material, wherein the magnetron sputtering coating process parameters are as follows: the current intensity is 4.1A, and the vacuum pressure is lower than 10 when the magnetron sputtering coating starts-3Pa, argon protection, and magnetron sputtering coating time of 5.8 hours; the magnetic field intensity control parameters of the equipment adopted by the magnetron sputtering coating are as follows: magnetic performance parameters of the single magnetic stripe: remanence (Br)1.21T, coercive force (Hcb)920KA/m, maximum magnetic energy product (BH)277KJ/m3(20 ℃ C.); the working temperature is 71 ℃, the diameter of the target material in the equipment adopted by magnetron sputtering coating is 55mm, the length of the target material is 720mm, the effective range is 620m, and the number of magnetic stripe channels in the target material is 4. The distance between the target and the composite material in the equipment adopted by magnetron sputtering coating is 47 mm.
According to the illustration in FIG. 1, Al plating with a thickness of about 21.2 μm is finally prepared on the surface of the epoxy resin-based composite material. The bonding strength of the metal plating layer and the substrate is 0.47 MPa. The ductility of the coating was 4%.
The film layers prepared by adopting the current intensity range lower than that adopted in the content of the invention of the specification all have the phenomenon of film layer cracking after the film coating is finished, and are judged to be waste products and cannot be used.
Example 2
A method for thickening a magnetron sputtering coating on the surface of a composite material comprises the following steps:
step 1, pre-cleaning a composite material to be plated, wherein the length of the composite material is 300mm, cleaning the surface of an epoxy resin-based material for 3 times by using an analytical ethanol reagent, and then drying the cleaned composite material to obtain the pre-cleaned epoxy resin-based material; the pre-cleaning aims to remove impurity components on the surface of the matrix, ensure the stability of a film forming interface and avoid the phenomena of bulging and cracking of a film layer caused by unclean composite material matrix. The drying process is vacuum drying, the vacuum degree is 18Pa, and the vacuum drying time is 2.8 hours; the temperature of vacuum drying is lower than the glass transition temperature of the epoxy resin;
step 2, preprocessing, namely preprocessing the aluminum target material and the epoxy resin base material after being preprocessed through glow discharge (current intensity is 1A, duration is 5min) generated by plasma, so as to obtain the preprocessed target material and the preprocessed epoxy resin base material; the glow treatment aims at preheating the target material and the substrate material, is favorable for increasing the layer-substrate bonding force and finally cleaning the substrate
Step 3, performing magnetron sputtering coating, namely performing magnetron sputtering coating on the pretreated epoxy resin base material by adopting the pretreated target material, wherein the magnetron sputtering coating process parameters are as follows: the current intensity is 3.9A, and the vacuum pressure is lower than 10 when the magnetron sputtering coating starts-3Pa, argon protection, and magnetron sputtering coating time of 6.1 hours; the magnetic field intensity control parameters of the equipment adopted by the magnetron sputtering coating are as follows: magnetic performance parameters of the single magnetic stripe: remanence (Br)1.18T, coercive force (Hcb)900KA/m, maximum magnetic energy product (BH)270KJ/m3(20 ℃ C.); the working temperature is 78 ℃, the diameter of the target material in the equipment adopted by the magnetron sputtering coating is 55mm, the length of the target material is 720mm, the effective range is 620mm, and the number of magnetic stripe channels in the target material is 4. The distance between the target and the composite material in the equipment adopted by magnetron sputtering coating is 42 mm.
Finally, an Al coating with the thickness of about 20.5 mu m is prepared on the surface of the epoxy resin-based composite material. The bonding strength of the metal plating layer and the substrate is 0.51 MPa. The ductility of the coating was 4%.
Example 3
A method for thickening a magnetron sputtering coating on the surface of a composite material comprises the following steps:
step 1, pre-cleaning a composite material to be plated, wherein the length of the composite material is 500mm, cleaning the surface of an epoxy resin-based material for 3 times by using an analytical ethanol reagent, and then drying the cleaned composite material to obtain the pre-cleaned epoxy resin-based material; the pre-cleaning aims to remove impurity components on the surface of the matrix, ensure the stability of a film forming interface and avoid the phenomena of bulging and cracking of a film layer caused by unclean composite material matrix. The drying process is vacuum drying, the vacuum degree is 18Pa, and the vacuum drying time is 2.5 hours; the temperature of vacuum drying is lower than the glass transition temperature of the epoxy resin;
step 2, preprocessing, namely preprocessing the aluminum target material and the epoxy resin base material after being preprocessed through glow discharge (current intensity is 1A, duration is 5min) generated by plasma, so as to obtain the preprocessed target material and the preprocessed epoxy resin base material; the glow treatment aims at preheating the target material and the substrate material, is favorable for increasing the layer-substrate bonding force and finally cleaning the substrate
Step 3, performing magnetron sputtering coating, namely performing magnetron sputtering coating on the pretreated epoxy resin base material by adopting the pretreated target material, wherein the magnetron sputtering coating process parameters are as follows: the current intensity is 3.1A, and the vacuum pressure at the beginning of magnetron sputtering coating is 7.8 multiplied by 10-4Pa, argon protection, and magnetron sputtering coating time of 8.4 hours; the magnetic field intensity control parameters of the equipment adopted by the magnetron sputtering coating are as follows: magnetic performance parameters of the single magnetic stripe: remanence (Br)1.18T, coercive force (Hcb)900KA/m, maximum magnetic energy product (BH)270KJ/m3(20 ℃ C.); the working temperature is 86 ℃, the diameter of the target material in the equipment adopted by the magnetron sputtering coating is 55mm, the length of the target material is 720mm, the effective range is 620mm, and the number of magnetic stripe channels in the target material is 4. The distance between the target and the composite material in the equipment adopted by magnetron sputtering coating is 42 mm.
Finally, an Al coating with the thickness of about 20.5 mu m is prepared on the surface of the epoxy resin-based composite material, and the bonding strength of the metal coating and the substrate is 0.26 MPa. The bonding strength was not satisfactory.
The reason for the failure of example 3 is that when the current intensity is too low, the ionization rate of the plasma in the vacuum chamber is low, the total amount of the plasma is small, the impedance value of the plasma is large, meanwhile, the ionization rate of the plasma is low, the sputtering voltage is low, the acceleration of charged particles bombarding the target material is insufficient, the final result is that the deposition rate is low, the bonding energy of the film layer and the substrate is low, and in order to reach the standard thickness of 20 μm, the deposition can only be completed by prolonging the coating time, but as can be seen from fig. 2, due to the low bonding energy, the preferred orientation degree of the Al (111) crystal plane is reduced, the preferred orientation of the Al (022) crystal plane is increased, and the quality of the film layer is not good.
Example 4
A method for thickening a magnetron sputtering coating on the surface of a composite material comprises the following steps:
step 1, pre-cleaning a composite material to be plated, wherein the length of the composite material is 500mm, cleaning the surface of an epoxy resin-based material for 3 times by using an analytical ethanol reagent, and then drying the cleaned composite material to obtain the pre-cleaned epoxy resin-based material; the pre-cleaning aims to remove impurity components on the surface of the matrix, ensure the stability of a film forming interface and avoid the phenomena of bulging and cracking of a film layer caused by unclean composite material matrix. The drying process is vacuum drying, the vacuum degree is 15Pa, and the vacuum drying time is 2.6 hours; the temperature of vacuum drying is lower than the glass transition temperature of the epoxy resin;
step 2, preprocessing, namely preprocessing the aluminum target material and the epoxy resin base material after being preprocessed through glow discharge (current intensity is 1A, duration is 5min) generated by plasma, so as to obtain the preprocessed target material and the preprocessed epoxy resin base material; the glow treatment aims at preheating the target material and the substrate material, is favorable for increasing the layer-substrate bonding force and finally cleaning the substrate
Step 3, performing magnetron sputtering coating, namely performing magnetron sputtering coating on the pretreated epoxy resin base material by adopting the pretreated target material, wherein the magnetron sputtering coating process parameters are as follows: the current intensity is 5.0A, and the vacuum pressure at the beginning of magnetron sputtering coating is 8.2 multiplied by 10-4Pa, argon protection, and magnetron sputtering coating time of 4.9 hours; the magnetic field intensity control parameters of the equipment adopted by the magnetron sputtering coating are as follows: magnetic performance parameters of the single magnetic stripe: remanence (Br)1.18T, coercive force (Hcb)900KA/m, maximum magnetic energy product (BH)270KJ/m3(20℃)；The working temperature is 75 ℃, the diameter of the target material in the equipment adopted by the magnetron sputtering coating is 55mm, the length of the target material is 720mm, the effective range is 620mm, and the number of magnetic stripe channels in the target material is 4. The distance between the target and the composite material in the equipment adopted by magnetron sputtering coating is 42 mm.
Finally, an Al coating with the thickness of about 20.1 mu m is prepared on the surface of the epoxy resin-based composite material. The phenomenon of bulging and cracking of the plating layer after being exposed in the air for 2 hours is directly judged to be waste.
Example 4 failed because when the current intensity was too high, the plasma ionization rate was high, and the plasma impedance value in the vacuum chamber was decreased to some extent, but according to ohm's law, the product of the current intensity and the plasma impedance value was still increased, resulting in an increase in sputtering voltage, and the acceleration of the charged particles bombarding the target was too high, and during the deposition of the coating, the deposited coating atoms were collided out while depositing, generating a large amount of heat and a large residual stress, while the internal stress of the magnetron sputtering film increased with the increase in thickness, and the bonding force decreased with the increase in coating thickness, and the final result was reflected in the film layer bulging and cracking. In addition, the standard thickness of 20 μm can be achieved only by reducing the coating time, but the temperature is too high due to the increase of the collision probability of atoms and the accumulation of heat, the outgassing phenomenon of the composite material is aggravated, and the O element reacts with Al atoms of the target material to generate Al2O3And the purity of the film layer is influenced.
Example 5
A method for thickening a magnetron sputtering coating on the surface of a composite material comprises the following steps:
step 1, pre-cleaning, wherein the length of a composite material to be plated is 500mm, cleaning the surface of an epoxy resin-based material for 3 times by using an ethanol analysis reagent, and then drying the cleaned composite material to obtain the pre-cleaned epoxy resin-based material; the pre-cleaning aims to remove impurity components on the surface of the matrix, ensure the stability of a film forming interface and avoid the phenomena of bulging and cracking of a film layer caused by unclean composite material matrix. The drying process is vacuum drying, the vacuum degree is 15Pa, and the vacuum drying time is 2.5 hours; the temperature of vacuum drying is lower than the glass transition temperature of the epoxy resin;
step 2, preprocessing, namely preprocessing the aluminum target material and the epoxy resin base material after being preprocessed through glow discharge (current intensity is 1A, duration is 5min) generated by plasma, so as to obtain the preprocessed target material and the preprocessed epoxy resin base material; the glow treatment aims at preheating the target material and the substrate material, is beneficial to increasing the layer-substrate bonding force and cleaning the substrate finally.
Step 3, performing magnetron sputtering coating, namely performing magnetron sputtering coating on the pretreated epoxy resin base material by adopting the pretreated target material, wherein the magnetron sputtering coating process parameters are as follows: the current intensity is 4.0A, and the vacuum pressure is lower than 10 when the magnetron sputtering coating starts-3Pa, argon protection, and magnetron sputtering coating time of 5.9 hours; the magnetic field intensity control parameters of the equipment adopted by the magnetron sputtering coating are as follows: magnetic performance parameters of the single magnetic stripe: remanence (Br)1.21T, coercive force (Hcb)920KA/m, maximum magnetic energy product (BH)277KJ/m3(20 ℃ C.); the working temperature is 71 ℃, the diameter of the target material in the equipment adopted by magnetron sputtering coating is 55mm, the length of the target material is 720mm, the effective range is 620m, and the number of magnetic stripe channels in the target material is 4. The distance between the target and the composite material in the equipment adopted by magnetron sputtering coating is 60 mm.
After the workpiece is taken out, the plating state is a bulging state and a cracking state, and the workpiece is judged to be an invalid part.
The reason for the failure of example 5 is that the distance between the target and the composite material substrate is too large, the energy of the target atoms is gradually reduced after being sputtered, and finally the bonding energy is too low to be worth of qualified film.
Before the magnetron sputtering process is adjusted, the length of the target material, the diameter of the target material, the internal magnetic field intensity of the target material, the number of magnetic stripes and the target-base distance need to be adjusted. The length and diameter of the target determine the same current intensity and have different current densities, and the current densities influence the deposition rate and the film forming quality.
The meaning and mechanistic explanation of the patent technology:
(1) when thicker metal coating is deposited, electroplating or chemical plating is mostly adopted, and cases and technologies for developing thicker coatings by adopting a direct current magnetron sputtering technology are rare. The significance of performing magnetron sputtering on the surface of an epoxy resin-based composite material is that the composite material belongs to a porous material, the composite material is required to be soaked in plating solution for electroplating or chemical plating, the plating solution and metal ions are easy to attach to pores, and the inside of the composite material is corroded after a certain time, so that the mechanical property of the composite material is reduced, the composite material is invalid, the service life and the reliability of the material are influenced, and therefore, an environment-friendly technology is required to be adopted.
(2) The bonding strength of the magnetron sputtering film layer and the substrate is reduced along with the increase of the thickness.
(3) The residual stress of the magnetron sputtering film layer is increased along with the increase of the thickness, and the film layer is inevitably subjected to the phenomena of bulging and cracking due to the excessive residual stress.
(4) The method for thickening the magnetron sputtering film layer comprises the steps of increasing the current intensity, increasing the deposition rate and not changing the film coating time. And the coating time is increased, and the deposition rate is unchanged. Thirdly, performing composite adjustment.
(5) Before the magnetron sputtering process is adjusted, the length of the target material, the diameter of the target material, the internal magnetic field intensity of the target material, the number of magnetic stripes and the target-base distance need to be adjusted.
(6) The length and diameter of the target determine the same current intensity and have different current densities, and the current densities influence the deposition rate and the film forming quality.
(7) The magnetic field intensity and the number of the magnetic strips determine the deflection degree of the plasmas in the vacuum cavity, determine the number of the bound plasmas in the target material and directly influence the impedance value of the plasmas.
(8) The target-base distance directly determines the deposition rate and initial binding energy, the plasma has a mean free path, the sputtering rate decays with increasing distance, and too large or too small a target-base distance has an effect on the binding strength and residual stress.
(9) The current intensity and the coating time are nonlinear to the change of the residual stress and the bonding strength of the film.
(10) When the current intensity is increased by a single factor, the ionization rate of the plasma is increased, and the plasmaThe volume impedance value is reduced, according to ohm law, the increasing trend of the product of the current intensity and the impedance value is gradually reduced, but the general trend is still increased, so that the sputtering voltage is increased along with the increase of the current intensity, the sputtering voltage is increased, the plasma acceleration is increased, the deposition rate is increased, according to the principle, the film layer is always deposited and collided by atoms with certain initial speed again, when the impact rate is too high, the performance of the film layer is reduced, and the residual stress is increased; meanwhile, the heat accumulation is increased due to too frequent atomic collision, the composite material gassing phenomenon is aggravated, and the O element reacts with the Al atom of the target material to generate Al2O3The phase has influence on the purity of the film layer, and is particularly represented by the appearance of Al with wider half peak in an XRD pattern2O3(012) Crystal face with high texture coefficient.
(11) When the coating time is prolonged by a single factor, for a thicker coating, when the current intensity is too low, the ionization rate of plasma in a vacuum cavity is lower, the total number of the plasma is less, the sputtering voltage is lower, the acceleration of charged particles bombarding a target material is insufficient, the deposition rate is lower, the bonding energy of a film layer and a substrate is lower, and the bonding strength is inevitably reduced. Meanwhile, the combination energy is lower, the crystal structure of the pure Al film is changed, the crystal crystallization process is always carried out in a mode of minimum energy, the result is that the preferred orientation degree of the Al (111) crystal face is reduced, the preferred orientation of the Al (022) crystal face is increased, and the research process finds that the combination strength value of the Al film is related to the high texture coefficient of the Al (111) crystal face.
(12) According to the principle of the analysis, the technological parameters can be obtained after the simple orthogonal test, and the parameter formulation can be completed through the adjustment of the current intensity and the coating time only after the parameters such as the length of the target material, the diameter of the target material, the magnetic field intensity inside the target material, the number of magnetic stripes, the target-substrate distance and the like are tested and determined.
(13) The pure Al plating layer with the thickness of more than 20 microns is prepared on the surface of the epoxy resin matrix composite material, and the problems of low bonding strength and overlarge internal stress are solved.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (11)
1. The method for thickening the magnetron sputtering coating on the surface of the composite material is characterized by comprising the following steps of:
step 1, pre-cleaning, namely cleaning the surface of the composite material by using an ethanol reagent, and then drying the cleaned composite material to obtain the pre-cleaned composite material;
step 2, preprocessing, namely preprocessing the target material and the preprocessed composite material by glow discharge generated by plasma to obtain a preprocessed target material and a preprocessed composite material;
step 3, performing magnetron sputtering coating, namely performing magnetron sputtering coating on the pretreated composite material by adopting the pretreated target material, wherein the magnetron sputtering coating process parameters are as follows: the current intensity is 3.8-4.2A, and the vacuum pressure is lower than 10 when the magnetron sputtering coating starts-3Pa, argon protection, and magnetron sputtering coating time of 5.5-6.5 hours; obtaining a composite material with a plating layer;
the composite material is an epoxy resin-based material.
2. The method for thickening a magnetron sputtering coating on a composite material surface according to claim 1, wherein the target is aluminum.
3. The method for thickening a magnetron sputtering coating on the surface of a composite material according to claim 1, wherein the ethanol reagent in the step 1 is analytically pure.
4. The method for thickening the magnetron sputtering coating on the surface of the composite material according to claim 1, wherein the drying process in the step 1 is vacuum drying, the vacuum degree is 1-20 Pa, and the vacuum drying time is 2-3 hours.
5. The method for thickening the magnetron sputtering coating on the surface of the composite material according to claim 4, wherein the drying process in the step 1 is vacuum drying, and the temperature of the vacuum drying is lower than the glass transition temperature of the composite material.
6. The method for thickening the magnetron sputtering coating on the surface of the composite material according to claim 1, wherein in the step 2, the current intensity in the glow discharge process is 0.8-1.2A, and the duration is 3-10 minutes.
7. The method for thickening the magnetron sputtering coating on the surface of the composite material according to claim 1, wherein in the step 3, the magnetic field intensity control parameters of equipment adopted by magnetron sputtering coating are as follows: magnetic performance parameters of the single magnetic stripe: remanence is 1.18-1.22T, coercive force is more than 876KA/m, and maximum magnetic energy product is 263-287 KJ/m3(20 ℃ C.); the working temperature is less than or equal to 80 ℃.
8. The method for thickening a magnetron sputtering coating on the surface of a composite material according to claim 1, wherein in the step 3, the magnetron sputtering coating adopts equipment in which the target is a cylindrical target, the diameter of the target is 45-55 mm, the length of the target is 600-800 mm, the effective length range of the target is 550-650 mm, and the number of magnetic stripe channels in the target is 4.
9. The method for thickening a magnetron sputtering coating on the surface of a composite material according to claim 8, wherein in the step 3, a distance between the target and the composite material in equipment for magnetron sputtering coating is 40-50 mm.
10. The method for thickening a magnetron sputtering coating on a composite material surface according to claim 8, wherein in the step 3, the length of the composite material to be coated does not exceed an effective length range of a target.
11. The method for thickening the magnetron sputtering coating on the surface of the composite material according to claim 1, wherein the thickness of the coating on the composite material with the coating is more than 20 μm, and the bonding strength between the coating and the composite material of the base material is more than 0.4 MPa.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114075657A (en) * | 2021-11-04 | 2022-02-22 | 核工业西南物理研究院 | Method for improving air tightness of resin-based composite material forming member |
| CN117832333A (en) * | 2024-03-05 | 2024-04-05 | 龙焱能源科技（杭州）有限公司 | Cadmium telluride thin film battery and preparation method thereof |
| CN117832333B (en) * | 2024-03-05 | 2024-05-31 | 龙焱能源科技（杭州）有限公司 | Cadmium telluride thin film battery and preparation method thereof |
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Application publication date: 20210820 |