CN113604852B - Anti-adhesion surface for rubber mold and preparation method and application thereof - Google Patents

Anti-adhesion surface for rubber mold and preparation method and application thereof Download PDF

Info

Publication number
CN113604852B
CN113604852B CN202110873628.2A CN202110873628A CN113604852B CN 113604852 B CN113604852 B CN 113604852B CN 202110873628 A CN202110873628 A CN 202110873628A CN 113604852 B CN113604852 B CN 113604852B
Authority
CN
China
Prior art keywords
adhesion
metal
adhesion surface
oil
micro
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
CN202110873628.2A
Other languages
Chinese (zh)
Other versions
CN113604852A (en
Inventor
刘灿森
庄明塔
揭晓华
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.)
Guangdong University of Technology
Original Assignee
Guangdong University of Technology
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 Guangdong University of Technology filed Critical Guangdong University of Technology
Priority to CN202110873628.2A priority Critical patent/CN113604852B/en
Publication of CN113604852A publication Critical patent/CN113604852A/en
Application granted granted Critical
Publication of CN113604852B publication Critical patent/CN113604852B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B29C33/3842—Manufacturing moulds, e.g. shaping the mould surface by machining
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/16—Pretreatment, e.g. desmutting
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • C25D11/246—Chemical after-treatment for sealing layers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

The invention belongs to the technical field of metal surface treatment, and discloses an anti-adhesion surface for a rubber mold, and a preparation method and application thereof. The anti-adhesion surface is formed by forming a micro-nano hole structure on the surface of a metal substrate, the micro-nano hole structure is in an irregular bending laminated shape, the aperture of the micro-hole structure is 50-150 nm, and the roughness of the anti-adhesion surface is Ra = 1-1.4 μm. The anti-adhesion surface is a metal matrix, the surface of the metal matrix is pretreated by an anodic oxidation method, and then the prepared anodic oxidation metal surface is placed in molten octadecanoic acid or/and hexadecanoic acid for soaking, and then is cleaned and dried; and adding lubricating oil with low surface tension to the surface of the soaked anodized metal to carry out vacuum oil loading treatment to obtain the anode material. The surface is of a micro-nano porous structure, has excellent self-cleaning property, adhesion resistance, corrosion resistance, high-temperature stability and reusability, and has good application prospect in the field of rubber molds.

Description

Anti-adhesion surface for rubber mold and preparation method and application thereof
Technical Field
The invention belongs to the technical field of metal surface treatment, and particularly relates to an anti-adhesion surface for a rubber mold as well as a preparation method and application thereof.
Background
The rubber mould is an extremely important mechanical device in the national economic industrial production process. However, the mold is often subject to adhesion of rubber, compounding agents, and mold release agents during service. Repeated use of contaminated molds can affect the appearance and quality of the tire product, and the molds must be cleaned or replaced periodically. Frequent disassembly and cleaning of the die seriously affect production efficiency, increase cost, and also cause resource waste and environmental pollution. In view of the above, the problem of contamination of the rubber mold is of great concern in the industry. At present, the adhesion problem of the die is mainly solved by adopting the treatment processes of cleaning, a release agent, polishing, nitriding, a Teflon coating, a CrN coating, a DLC coating and the like. However, the cleaning technology focuses on the cleaning efficiency after the adhesion is generated, so that the problem of addressing both the symptoms and root causes is solved, and the problem that the rubber mold needs to be frequently disassembled and cleaned during production cannot be fundamentally solved; the release agent has short service cycle, needs frequent spraying and can cause corrosion and pollution to the die; the superfinishing and polishing is very limited in improving the desorption effect of the surface of the die and high in processing and manufacturing cost; nitriding can improve the wear resistance and corrosion resistance of the die to a certain extent, but cannot effectively solve the problem of die pollution; the Teflon coating has low hardness and poor wear resistance, is easy to lose efficacy due to scratch and abrasion, and contains substances harmful to human bodies and the environment; although the CrN coating has good wear resistance and corrosion resistance, the surface roughness of the CrN coating is large, and the friction coefficient of the CrN coating with rubber is relatively large, so that the vulcanization resistance in the rubber vulcanization process is large, and the vulcanization quality is reduced. Although the DLC coating has higher hardness and good wear-resistant and antifriction properties, the DLC coating has thinner thickness, low bonding strength with a substrate and higher friction coefficient compared with rubber. The DLC coating and the rubber are mainly composed of hydrocarbon elements and have similar polarity. The similar compatibility of the two components further improves the adhesion between the two components. In addition, the preparation of CrN and DLC coatings involves extremely complex process, expensive equipment and high energy and material consumption. Based on the method, the anti-adhesion surface of the rubber mold is simple, efficient, green and environment-friendly, and is easy to realize large-scale industrial production. The prepared surface has excellent adhesion resistance, corrosion resistance, high-temperature stability and reusability, and has good application prospect in the field of adhesion pollution resistance of rubber molds.
Disclosure of Invention
In order to solve the above-mentioned drawbacks and drawbacks of the prior art, it is an object of the present invention to provide an anti-adhesion surface for a rubber mold. The surface is formed with a micropore structure on the surface of a metal matrix, the micro-nano pore structure is in an irregular bending laminated shape, a plurality of bulges are respectively arranged on the inner wall of the micro-nano pore structure, the aperture of the micro-nano pore structure is 50-150 nm, and the micro-nano pore structure has excellent adhesion resistance, corrosion resistance, high-temperature stability and reusability.
The invention also aims to provide a preparation method of the anti-adhesion surface for the rubber mold. The method comprises the steps of grinding and polishing the surface of a metal mold substrate, ultrasonically cleaning, then drying in vacuum, and treating the surface of the metal substrate by an anodic oxidation method. Placing the anodized metal matrix into molten low-surface fatty acid for soaking, placing the soaked metal matrix into an oven, and loading oil with low surface tension under a vacuum condition to prepare the anti-adhesion surface of the rubber mold. Simple, efficient, green and environment-friendly, and is easy to realize large-scale industrial production.
It is a further object of the present invention to provide the use of an anti-adhesion surface for the above mold.
The purpose of the invention is realized by the following technical scheme:
an anti-adhesion surface for a rubber mold is characterized in that a micro-nano hole structure is formed on the surface of a metal substrate, the micro-nano hole structure is in an irregular bending laminated shape, a plurality of bulges are arranged on the inner wall of the micro-nano hole structure respectively, and the aperture of the micro-nano hole structure is 50-150 nm; the roughness of the adhesion-resistant surface is Ra =1 to 1.4 μm.
Preferably, the anti-adhesion surface is prepared by grinding and polishing the surface of a metal matrix, placing the metal matrix in a solvent for ultrasonic cleaning, then drying in vacuum, placing the pretreated metal matrix in phosphoric acid solution electrolyte with the concentration of 50-80 g/L, taking a graphite sheet or a platinum sheet as a cathode and the metal matrix as an anode, and setting the anodic oxidation parameters as follows: the current density is 25-35A/dm 2 The time is 15-25 min, the temperature is 15-25 ℃, the distance between the two electrodes is 25-35 mm, the surface of the prepared anodic oxide metal is placed in molten octadecanoic acid or/and hexadecanoic acid for soaking, and then the anodic oxide metal is cleaned by ultrasound and dried; finally, lubricating oil with low surface tension is dripped on the surface of the anode oxidation metal subjected to soaking treatment to carry out vacuum oil carrying treatment to obtain the anode oxidation metal; the oil carrying capacity of the surface of the anode oxidation metal subjected to soaking treatment is 6-10 mu L/cm 2 。
Preferably, the metal matrix is a die steel or aluminum alloy die; the surface roughness of the pretreated metal substrate is Ra = 0.05-0.1 μm.
Preferably, the low surface tension lubricating oil is a perfluorinated oil or/and a silicone oil.
More preferably, the perfluorinated oil is perfluoropolyether FX-5200, perfluoropolyether Krytox 100, or perfluorotripentylamine FC-70.
More preferably, the volume ratio of the perfluorinated oil to the silicone oil is (0.5-1): 1.
The preparation method of the anti-adhesion surface for the tire mold comprises the following specific steps:
s1, grinding and polishing the surface of a metal matrix, placing the metal matrix in a solvent for ultrasonic cleaning, and then drying in vacuum to obtain a pretreated metal matrix;
s2, placing the pretreated metal matrix in oxalic acid solution electrolyte with the concentration of 50-80 g/L, taking a graphite sheet or a platinum sheet as a cathode and the metal matrix as an anode, and setting anodic oxidation parameters: the current density is 25-35A/dm 2 The time is 15-25 min, the temperature is 15-25 ℃, the distance between two electrodes is 25-35 mm, and the anode oxidized metal surface is prepared by naturally airing after solvent ultrasonic cleaning;
s3, placing the surface of the anodized metal in molten low-surface-energy fatty acid for soaking, then carrying out ultrasonic cleaning by using a solvent, and naturally airing; then the mixture is loaded into lubricating oil with low surface tension in vacuum, and the oil loading parameters are set to prepare the anti-adhesion surface.
Preferably, the solvents in steps S1, S2 and S3 are all absolute ethyl alcohol or/and deionized water.
Preferably, the soaking time in the step S3 is 10-20 min, and the ultrasonic cleaning time is 1-3 min.
The surface anti-adhesion agent is applied to the field of preparation of rubber molds. A micro-nano porous structure is formed on the surface of the substrate, so that the low-surface-energy lubricating oil can be stored well. The surface modified by the low surface substance has better compatibility with the lubricating oil with low surface tension, meanwhile, the micro-nano porous structure provides a storage space, the oil is not easy to run off, when a rubber product is prepared, an oil film formed on the surface of a metal mold is beneficial to resisting the adhesion of vulcanized rubber, the rubber mold is easier to demold, and the rubber mold can be applied to the environment of 90-200 ℃, and is preferably applied to the environment of 120-190 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method of the anti-adhesion surface provided by the invention is simple and adjustable to operate, is efficient and low in cost, and the used reagent and the preparation process have no pollution to the environment and no harm to operators, and are easy to realize large-scale industrial production.
2. The low surface tension oil film covered by the anti-adhesion surface of the rubber mold enables the surface of the rubber mold to be smooth and to have low surface energy, so that the surface is endowed with excellent anti-adhesion performance. The surface of the oil-absorbing material has a micro-nano porous structure, can be more effectively adsorbed and stored by being modified by a low surface energy substance, has low surface energy, and further improves the performance and prolongs the service life of the oil-absorbing material. In addition, recycling can be achieved by simply adding a low surface tension lubricating oil to the surface.
3. The surface of the micro-nano porous structure prepared by the method has excellent self-cleaning property, adhesion resistance, corrosion resistance, high-temperature stability and reusability. Has good application prospect in the field of adhesion pollution resistance of rubber molds.
Drawings
FIG. 1 is a schematic diagram of the morphology and structure of the anti-adhesion surface of the rubber mold prepared by the present invention;
FIG. 2 is a photograph of the water contact angle of the anti-adhesion surface of the rubber mold prepared in example 1;
FIG. 3 is a photograph showing the self-cleaning effect of the adhesion-resistant surface of the rubber mold prepared in example 1;
FIG. 4 is a front and rear photograph of the anti-hot water of the anti-adhesion surface of the rubber mold prepared in example 1;
FIG. 5 is a photograph of the anti-adhesive surface of the rubber mold prepared in example 1, which was subjected to a rubber vulcanization test.
FIG. 6 shows the adhesion-preventing surfaces of the rubber molds and the metal substrates prepared in example 1 at 0.05mol/L H 2 SO 4 Polarization curve in solution.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. The reagents, methods and apparatus employed in the present invention are conventional in the art, except as otherwise indicated.
Example 1
1. The surface of 6082 aluminum alloy is ground and polished by sand paper of 600-2000 meshes (Ra = 0.05-0.1 μm), then the substrate is sequentially placed into absolute ethyl alcohol and deionized water for ultrasonic cleaning, and finally the substrate is placed into an oven for vacuum drying for standby.
2. And (3) putting the substrate treated in the step (1) as an anode into 40g/L phosphoric acid electrolyte, wherein the cathode is aluminum alloy with the same area as the anode, the distance between the two electrodes is 20mm, and the temperature of the electrolyte is 10 ℃. Setting anodic oxidation current density at 20A/dm 2 And the time is 10min. And putting the metal surface subjected to anodic oxidation treatment into deionized water for ultrasonic cleaning, and naturally airing for later use.
3. And (3) soaking the anodized metal surface treated in the step (2) in molten palmitic acid (hexadecanoic acid) for 20min, and then placing the soaked surface in absolute ethyl alcohol for ultrasonic cleaning for 2min.
4. Dropping Krytox 100 on the metal surface treated in the step 3, and then putting the metal surface into an oven for vacuum oil loading treatment, wherein the oil loading is 5.8 mu L/cm 2 And carrying oil for 60min to obtain the anti-adhesion surface. The static contact angle of the surface was 116 °.
Example 2
1. The surface of 6082 aluminum alloy of a metal mold base body is ground and polished by 600-2000-mesh sand paper to enable the surface roughness to be Ra = 0.05-0.1 mu m, then the base body is sequentially placed into absolute ethyl alcohol and deionized water for ultrasonic cleaning, and finally the base body is placed into an oven for vacuum drying for later use.
2. And (3) putting the substrate treated in the step (1) as an anode into a 50g/L phosphoric acid electrolyte, wherein the cathode is aluminum alloy with the same area as the anode, the distance between the two electrodes is 25mm, and the temperature of the electrolyte is 15 ℃. Setting the anodic oxidation current density at 25A/dm 2 And the time is 15min. And (3) putting the metal surface subjected to the anodic oxidation treatment into deionized water for ultrasonic cleaning, and naturally airing for later use.
3. And (3) soaking the anodized metal surface treated in the step (2) in molten palmitic acid (hexadecanoic acid) for 20min, and then placing the soaked surface in absolute ethyl alcohol for ultrasonic cleaning for 2min.
4. Dropping Krytox 100 on the metal surface treated in the step 3, and then putting the metal surface into an oven for vacuum oil loading treatment, wherein the oil loading is 6 mu L/cm 2 And carrying oil for 50min to obtain the anti-adhesion surface. The roughness of the adhesion-resistant surface is Ra =1 to 1.4 μm.
FIG. 1 is an SEM photograph of the morphology structure of the anti-adhesion surface of the rubber mold prepared by the invention. As can be seen from FIG. 1, a micro-nano porous structure is formed on the surface of the base body after anodic oxidation, so that the lubricating oil with low surface tension can be stored well. The surface modified by the low-surface substance has better compatibility with the lubricating oil with low surface tension, the micro-nano pore structure is in an irregular bending laminated shape, meanwhile, the micro-nano porous structure (with the pore diameter of 50-150 nm) provides a storage space, oil is not easy to run off, and an oil film formed on the surface is beneficial to resisting the adhesion of vulcanized rubber. FIG. 2 is a water contact angle and a static contact angle exceeding 118 ℃ of the adhesion-resistant surface of the rubber mold prepared in example 1, which shows that the surface has excellent hydrophobic properties. FIG. 3 is a photograph showing the self-cleaning effect of the anti-adhesion surface of the rubber mold prepared in example 1, and from FIG. 3, it can be seen that water drops roll off and carry away contaminants on the surface, indicating that the prepared surface has good self-cleaning property. Fig. 4 is a graph of the anti-adhesion surface of the rubber mold prepared in example 1 before (a) and after (b) the high temperature hot water resistance test. The surface of the micro-nano porous structure is dripped with blue hot water at about 90 ℃, and the surface of the micro-nano porous structure is dripped with blue hot water, and the droplets are not adhered with colors after sliding on the surface, so that the dyed high-temperature hot water does not leave any trace on the surface, and the prepared surface has excellent high-temperature resistance and also has anti-adhesion property at high temperature. FIG. 5 is a photograph of the anti-adhesion surface of the rubber mold prepared in example 1 after the vulcanization test, and from FIG. 5, it can be seen that the surface is clean as new and there is no trace of adhesion of the rubber, indicating that the surface has excellent anti-adhesion properties. FIG. 6 shows the adhesion-preventing surface of the rubber mold prepared in example 1 and the metal mold base at 0.05mol/L H 2 SO 4 Polarization curves in solution, as can be seen in FIG. 6, of the metal matrixThe self-corrosion potential is-549 mV, and the self-corrosion current is 2.15X10 -5 A/cm 2 . The self-corrosion potential of the prepared anti-adhesion surface with the micro-nano structure is-143 mV, and the self-corrosion current is 1.84X10 -8 A/cm 2 . The anti-adhesion surface of the rubber mold prepared by the invention has obviously lower self-corrosion current and higher self-corrosion potential, which shows that the corrosion resistance of the surface is obviously higher than that of a metal matrix. Therefore, the surface of the micro-nano porous structure prepared by the method has excellent self-cleaning property, adhesion resistance, corrosion resistance, high-temperature stability and reusability, and can be applied to the environment of 90-200 ℃.
Example 3
1. And (3) grinding and polishing the surface of the metal mold base body by using 600-2000-mesh sand paper, then sequentially putting the base body into absolute ethyl alcohol and deionized water for ultrasonic cleaning, and finally putting the base body into an oven for vacuum drying for later use.
2. And (3) putting the substrate treated in the step (1) as an anode into a 50g/L phosphoric acid electrolyte, wherein the cathode is aluminum alloy with the same area as the anode, the distance between the two electrodes is 30mm, and the temperature of the electrolyte is 15 ℃. Setting anodic oxidation current density at 25A/dm 2 And the time is 20min. And (3) putting the metal surface after the anodic oxidation treatment into deionized water for ultrasonic cleaning, and naturally airing for later use.
3. And (3) soaking the anodized metal surface treated in the step (2) in molten stearic acid (octadecanoic acid) for 15min, and then placing the soaked surface in absolute ethyl alcohol for ultrasonic cleaning for 2min.
4. Dripping full FC-70 on the metal surface treated in the step 3, and then putting the metal surface into an oven for vacuum oil loading treatment, wherein the oil loading is 6.5 mu L/cm 2 And carrying oil for 30min to obtain the anti-adhesion surface of the rubber mold. The roughness of the anti-adhesion surface is Ra = 1-1.4 μm, the static contact angle is 116 degrees, and the test result of the surface experiment of the prepared micro-nano porous structure is the same as that of the example 2, which shows that the surface of the micro-nano porous structure has excellent self-cleaning property, anti-adhesion property, corrosion resistance, high-temperature stability and reusability, and can be applied to the environment of 90-200 ℃.
Example 4
1. Grinding and polishing the surface of the metal mold base body by using 600-2000-mesh sand paper; and then sequentially putting the matrix into absolute ethyl alcohol and deionized water for ultrasonic cleaning, and finally putting the matrix into an oven for vacuum drying for later use.
2. And (3) putting the substrate treated in the step (1) as an anode into 60g/L phosphoric acid electrolyte, wherein the cathode is aluminum alloy with the same area as the anode, the distance between the two electrodes is 25mm, and the temperature of the electrolyte is 20 ℃. Setting anodic oxidation current density at 30A/dm 2 And the time is 20min. And (3) putting the metal surface after the anodic oxidation treatment into deionized water for ultrasonic cleaning, and naturally airing for later use.
3. And (3) soaking the anodized metal surface treated in the step (2) in molten stearic acid (octadecanoic acid) for 15min. And then putting the soaked surface into absolute ethyl alcohol for ultrasonic cleaning for 3min.
4. Dropwise adding silicone oil to the metal surface treated in the step 3, and then putting the metal surface into an oven for vacuum oil loading treatment, wherein the oil loading amount is 7 mu L/cm 2 And the oil loading time is 45min, so that the anti-adhesion surface of the rubber mold can be obtained. The roughness of the anti-adhesion surface is Ra = 1-1.4 μm, the static contact angle is 113 degrees, and the experimental test result of the surface of the prepared micro-nano porous structure is the same as that of the example 2, which shows that the surface of the micro-nano porous structure has excellent self-cleaning property, anti-adhesion property, corrosion resistance, high-temperature stability and reusability.
Example 5
1. And (3) grinding and polishing the surface of the metal mold base body by using 600-2000-mesh sand paper, then sequentially putting the base body into absolute ethyl alcohol and deionized water for ultrasonic cleaning, and finally putting the base body into an oven for vacuum drying for later use.
2. And (2) putting the matrix treated in the step (1) serving as an anode into 70g/L phosphoric acid electrolyte, wherein the cathode is aluminum alloy with the same area as the anode, the distance between the two electrodes is 35mm, and the temperature of the electrolyte is 25 ℃. Setting anodic oxidation current density at 25A/dm 2 And the time is 25min. The metal surface after the anodic oxidation treatment is put into deionized water for ultrasonic cleaning, and naturallyAnd (5) drying for later use.
3. And (3) soaking the anodized metal surface treated in the step (2) in molten palmitic acid (hexadecanoic acid) for 10min. And then putting the soaked surface into absolute ethyl alcohol for ultrasonic cleaning for 1min.
4. Dropwise adding silicone oil to the metal surface treated in the step (3), and then putting the metal surface into an oven for vacuum oil loading treatment, wherein the oil loading amount is 9 mu L/cm 2 And carrying oil for 30min to obtain the anti-adhesion surface of the rubber mold. The roughness of the anti-adhesion surface is Ra = 1-1.4 μm, the static contact angle is 106 °, and the experimental test result of the surface of the prepared micro-nano porous structure is the same as that of the example 2, which shows that the surface of the micro-nano porous structure has excellent self-cleaning property, anti-adhesion property, corrosion resistance, high-temperature stability and reusability.
Example 6
1. And (2) grinding and polishing the surface of the metal mold matrix by using 600-2000-mesh sand paper, then sequentially putting the matrix into absolute ethyl alcohol and deionized water for ultrasonic cleaning, and finally putting the matrix into an oven for vacuum drying for later use.
2. And (3) putting the substrate treated in the step (1) as an anode into a 50g/L phosphoric acid electrolyte, wherein the cathode is aluminum alloy with the same area as the anode, the distance between the two electrodes is 30mm, and the temperature of the electrolyte is 15 ℃. Setting the anodic oxidation current density at 25A/dm 2 The time is 20min. And (3) putting the metal surface subjected to the anodic oxidation treatment into deionized water for ultrasonic cleaning, and naturally airing for later use.
3. And (3) soaking the anodized metal surface treated in the step (2) in molten stearic acid (octadecanoic acid) for 15min, and then placing the soaked surface in absolute ethyl alcohol for ultrasonic cleaning for 2min.
4. Dropwise adding silicone oil to the metal surface treated in the step 3, and then putting the metal surface into an oven for vacuum oil loading treatment, wherein the oil loading amount is 8 mu L/cm 2 And carrying oil for 30min to obtain the anti-adhesion surface of the rubber mold. The roughness of the anti-adhesion surface is Ra = 1-1.4 μm, the static contact angle is 110 degrees, and the experimental test result of the surface of the prepared micro-nano porous structure is the same as that of the example 2, which shows that the surface of the micro-nano porous structure has excellent self-cleaning performanceAdhesion resistance, corrosion resistance, high temperature stability and recyclability.
Example 7
1. And (3) grinding and polishing the surface of the metal mold base body by using 600-2000-mesh sand paper, then sequentially putting the base body into absolute ethyl alcohol and deionized water for ultrasonic cleaning, and finally putting the base body into an oven for vacuum drying for later use.
2. And (3) putting the substrate treated in the step (1) as an anode into a 50g/L phosphoric acid electrolyte, wherein the cathode is aluminum alloy with the same area as the anode, the distance between the two electrodes is 30mm, and the temperature of the electrolyte is 15 ℃. Setting anodic oxidation current density at 25A/dm 2 And the time is 20min. And (3) putting the metal surface after the anodic oxidation treatment into deionized water for ultrasonic cleaning, and naturally airing for later use.
3. And (3) soaking the anodized metal surface treated in the step (2) in molten stearic acid (octadecanoic acid) for 15min, and then placing the soaked surface in absolute ethyl alcohol for ultrasonic cleaning for 2min.
4. Dropping Krytox 100 and silicone oil according to the volume ratio of (0.5-1) to 1 on the metal surface treated in the step 3, and then placing the metal surface into an oven for vacuum oil loading treatment, wherein the oil loading is 10 mu L/cm 2 And carrying oil for 30min to obtain the anti-adhesion surface of the rubber mold. The roughness of the anti-adhesion surface is Ra = 1-1.4 μm, the static contact angle is 103 degrees, and the experimental test result of the surface of the prepared micro-nano porous structure is the same as that of the example 2, which shows that the surface of the micro-nano porous structure has excellent self-cleaning property, anti-adhesion property, corrosion resistance, high-temperature stability and reusability.
The micro-nano porous structure is formed on the surface of the substrate, so that the low-surface-energy lubricating oil can be stored well. The surface modified by the low surface substance has better compatibility with the lubricating oil with low surface tension, meanwhile, the micro-nano porous structure provides a storage space, the oil is not easy to run off, when a rubber product is prepared, an oil film formed on the surface of the metal mold is beneficial to resisting the adhesion of vulcanized rubber, and the rubber mold is easier to demold. The static contact angle of the surface is 103-118 degrees, and the oil carrying capacity of the surface of the anodic oxidation metal subjected to soaking treatment is 6-10 mu L/cm 2 . Wherein, when the lubricating oil with low surface tension is silicone oil, the oil loading on the surface of the anodized metal subjected to soaking treatment reaches 7 mu L/cm 2 The above. Therefore, the surface of the micro-nano porous structure prepared by the method has excellent self-cleaning property, adhesion resistance, corrosion resistance, high-temperature stability and reusability, and can be applied to the environment of 90-200 ℃, preferably the environment of 120-190 ℃.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.

Claims (6)

1. A preparation method of an anti-adhesion surface for a rubber mold is characterized by comprising the following specific steps:
s1, grinding and polishing the surface of a metal matrix, placing the metal matrix in a solvent for ultrasonic cleaning, and then drying in vacuum to obtain a pretreated metal matrix; the metal matrix is die steel or aluminum alloy; the surface roughness of the pretreated metal matrix is Ra =0.05 to 0.1 mu m;
s2, placing the pretreated metal matrix in phosphoric acid solution electrolyte with the concentration of 50-80g/L, taking a graphite sheet or a platinum sheet as a cathode and the metal matrix as an anode, and setting anodic oxidation parameters: the current density is 25 to 35A/dm 2 Carrying out ultrasonic cleaning by using a solvent, and naturally airing to prepare an anodized metal surface, wherein the time is 15 to 25min, the temperature is 15 to 25 ℃, and the distance between the two electrodes is 25 to 35mm;
s3, placing the surface of the anodized metal in molten octadecanoic acid or/and hexadecanoic acid for soaking, then carrying out ultrasonic cleaning by using a solvent, and naturally airing; then loading the lubricating oil into lubricating oil with low surface tension in vacuum, and setting oil loading parameters to prepare an anti-adhesion surface; the lubricating oil with low surface tension is perfluorinated oil or/and silicone oil; the anti-adhesion surface is formed by forming a micro-nano hole structure on the surface of a metal matrix, the micro-nano hole structure is in an irregular bending laminated shape, and the aperture of the micro-nano hole structure is 50 to 150nm; the roughness of the anti-adhesion surface is Ra =1 to 1.4 [ mu ] m.
2. The method for preparing an anti-adhesion surface for a rubber mold according to claim 1, wherein the solvents in steps S1, S2 and S3 are all absolute ethyl alcohol or/and deionized water.
3. The method for preparing the anti-adhesion surface of the rubber mold as defined in claim 1, wherein the soaking time in the step S3 is 10 to 20min, and the ultrasonic cleaning time is 1 to 3min.
4. The method for producing an anti-adhesion surface for a rubber mold according to claim 1, wherein the perfluorinated oil in step S3 is perfluoropolyether FX-5200, perfluoropolyether Krytox 100, or perfluorotriamylamine FC-70, and the volume ratio of the perfluorinated oil to the silicone oil is (0.5-1: 1; the oil carrying capacity of the anti-adhesion surface is 6 to 10 mu L/cm 2 。
5. An anti-adhesion surface for a rubber mold, wherein the anti-adhesion surface is prepared by the method of any one of claims 1-4.
6. Use of the anti-adhesion surface according to claim 5 in the field of the preparation of rubber moulds.
CN202110873628.2A 2021-07-30 2021-07-30 Anti-adhesion surface for rubber mold and preparation method and application thereof Active CN113604852B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110873628.2A CN113604852B (en) 2021-07-30 2021-07-30 Anti-adhesion surface for rubber mold and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110873628.2A CN113604852B (en) 2021-07-30 2021-07-30 Anti-adhesion surface for rubber mold and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113604852A CN113604852A (en) 2021-11-05
CN113604852B true CN113604852B (en) 2022-12-20

Family

ID=78338796

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110873628.2A Active CN113604852B (en) 2021-07-30 2021-07-30 Anti-adhesion surface for rubber mold and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113604852B (en)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014003508A1 (en) * 2014-03-14 2015-09-17 Airbus Defence and Space GmbH Process for the preparation and use of a polished nanostructured metallic surface with water and ice-repellent properties
CN103882495B (en) * 2014-04-16 2017-10-27 山东理工大学 A kind of method that electrolytic plasma prepares aluminium alloy anti-adhesive surface
CN110129855B (en) * 2019-06-11 2021-04-27 南通大学 Surface treatment method for corrosion prevention of aluminum alloy

Also Published As

Publication number Publication date
CN113604852A (en) 2021-11-05

Similar Documents

Publication Publication Date Title
CN106736306B (en) Metal shell of electronic product and surface treatment method thereof
WO2011118583A1 (en) Anodizing device, treatment tank, method for producing roll-shaped mold for imprinting, and method for producing article having plurality of protruding parts on surface
TWI577837B (en) Surface treatment method for aluminum or aluminum alloy and aluminum article made thereby
CN105855151A (en) Long-acting hydrophobic-oleophobic surface treatment process
CN103722668A (en) Metal-plastic composite mobile phone shell and forming method thereof
CN108624925B (en) Composite preparation method of magnesium alloy surface super-hydrophobic structure
CN113636758A (en) Preparation method of ultrathin glass, ultrathin glass and application
CN113604852B (en) Anti-adhesion surface for rubber mold and preparation method and application thereof
CN108312419B (en) Surface-treated stainless steel, stainless steel resin complex and preparation method thereof
CN115029768A (en) Particulate matter applied to metal piece solid electrolytic polishing and application method
JP2006264225A (en) Shaping mold for urethane and surface treating method of shaping mold for urethane
CN104875440B (en) A kind of multicoat composite with magnesium/magnesium alloy as matrix and preparation method thereof
KR101481143B1 (en) Plating method of CFRP and CFRP roller plated thereof
CN103882495A (en) Method for preparing aluminum alloy anti-adhesive surface by electrolyzing plasma
CN110144611B (en) Magnesium alloy surface corrosion-resistant wear-resistant composite coating and preparation method thereof
JP4783124B2 (en) A method for forming a lubricating film.
CN102626971B (en) Method for manufacturing rubber roll of stretching straightening machine
CN208776860U (en) A kind of electroplating device
CN115365076B (en) Quick draining device for miniature steel balls
CN114889040B (en) Method for manufacturing composite gear
CN101327655A (en) Novel plastic coating technique for surface of non-tower water feeder pot body
CN113551963B (en) Method for preparing metallographic specimen of stainless steel ultrathin precise strip steel cross section
CN103911567A (en) Method for preparing an aluminum alloy adhesion-resistant surface based on ball throwing-anodic oxidation composite method
CN215239909U (en) Notebook shell burnishing device for anodic oxidation
CN102615036A (en) Method for preparing steel matrix high-adhesion super-hydrophobic surface

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