CN116837428A - Polymer mandrel micro-electroforming forming method based on in-situ autogenous conductive particles - Google Patents
Polymer mandrel micro-electroforming forming method based on in-situ autogenous conductive particles Download PDFInfo
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- CN116837428A CN116837428A CN202310995212.7A CN202310995212A CN116837428A CN 116837428 A CN116837428 A CN 116837428A CN 202310995212 A CN202310995212 A CN 202310995212A CN 116837428 A CN116837428 A CN 116837428A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 93
- 239000002245 particle Substances 0.000 title claims abstract description 68
- 238000005323 electroforming Methods 0.000 title claims abstract description 60
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 52
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 239000000243 solution Substances 0.000 claims abstract description 41
- 229920001690 polydopamine Polymers 0.000 claims abstract description 34
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 229960003638 dopamine Drugs 0.000 claims abstract description 11
- 238000006722 reduction reaction Methods 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 239000007853 buffer solution Substances 0.000 claims abstract description 4
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000011282 treatment Methods 0.000 claims description 29
- 239000011268 mixed slurry Substances 0.000 claims description 18
- 238000001723 curing Methods 0.000 claims description 14
- 229910021645 metal ion Inorganic materials 0.000 claims description 13
- 238000004070 electrodeposition Methods 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 5
- 230000000149 penetrating effect Effects 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000004080 punching Methods 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 238000013035 low temperature curing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000007872 degassing Methods 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 14
- 239000007788 liquid Substances 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 5
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 35
- 238000010586 diagram Methods 0.000 description 23
- 229910052759 nickel Inorganic materials 0.000 description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 229910000863 Ferronickel Inorganic materials 0.000 description 7
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 230000010076 replication Effects 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 3
- 229940081974 saccharin Drugs 0.000 description 3
- 235000019204 saccharin Nutrition 0.000 description 3
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000176 sodium gluconate Substances 0.000 description 2
- 235000012207 sodium gluconate Nutrition 0.000 description 2
- 229940005574 sodium gluconate Drugs 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229920001486 SU-8 photoresist Polymers 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000002707 nanocrystalline material Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 229940074439 potassium sodium tartrate Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/10—Moulds; Masks; Masterforms
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
Abstract
The invention discloses a polymer mandrel micro-electroforming forming method based on in-situ autogenous conductive particles, which comprises the following steps: 1. putting the polydimethylsiloxane prepolymer into a dopamine-containing tris hydrochloride buffer solution to graft a polydopamine layer; 2. adding a solution containing metal ions-reducing agent into the polydopamine modified prepolymer, and generating conductive particles in situ in the prepolymer; 3. mixing a prepolymer containing conductive particles and a curing agent, pouring the mixture onto the surface of an original template, and curing and forming to prepare a polymer core mold; 4. immersing the polymer core mould into electroforming liquid, and preparing the metal micro-part by micro-electroforming; 5. and (5) post-treating the metal micro parts. The invention generates conductive particles in situ in the polymer through reduction reaction, realizes the reliable preparation of the micro electroforming mandrel with high precision, low cost and repeated use, solves the problems of high preparation cost, short service life and the like of the existing photoresist mandrel, improves the preparation efficiency of the metal micro part and reduces the preparation cost.
Description
Technical Field
The invention belongs to the technical field of micro-manufacturing forming, and particularly relates to a polymer mandrel micro-electroforming forming method based on in-situ autogenous conductive particles.
Background
The micro electroforming technology has the advantages of high replication precision and repetition precision, wide material application range, low cost, capability of preparing nanocrystalline materials and the like, and becomes one of the key technologies for manufacturing metal micro parts at present. The preparation of metal micro-parts using micro-electroforming techniques typically involves the following steps: replication forming of a micro-electroforming mandrel, preparation of electroforming liquid, electrodeposition of metal ions, demolding and post-treatment of metal micro-parts, wherein the quality of the micro-electroforming mandrel determines the forming precision of the micro-electroforming technology, and a high-quality micro-electroforming mandrel is a prerequisite for preparing the metal micro-parts.
At present, a micro electroforming mandrel is generally formed by adhering an SU-8 photoresist microstructure prepared by photoetching or ion etching technology to a conductive substrate, and in the preparation process, large-scale expensive photoetching equipment and a complex preparation process are needed, and swelling phenomenon exists in electroforming liquid of the photoresist microstructure, so that the size replication precision of a metal micro part prepared by micro electroforming is low. Meanwhile, in the demolding process of the metal micro part, the photoresist microstructure needs to be dissolved and removed, and the mandrel is limited to single use. These disadvantages have limited the widespread use of micro-electroforming techniques to some extent.
Therefore, a new method is explored to prepare the reusable micro electroforming mandrel with short flow, low cost and high precision, and the combination of micro electroforming to prepare high-quality metal micro parts has important significance.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a polymer mandrel micro-electroforming method based on in-situ autogenous conductive particles aiming at the defects of the prior art. According to the method, polydopamine modification of a polydimethylsiloxane prepolymer, in-situ generation of conductive particles, mandrel solidification forming, micro electroforming forming, demoulding and post-treatment of a metal micro part are sequentially adopted, the conductive particles are generated in situ in the polydimethylsiloxane based body through the auxiliary reduction effect of polydopamine on metal ions, excellent replication forming precision and conductivity are endowed to the mandrel, and then the micro metal part is prepared by combining with a micro electroforming technology, so that the preparation cost of the metal micro part is reduced, and the preparation efficiency is improved.
In order to solve the technical problems, the invention adopts the following technical scheme: a polymer mandrel micro-electroforming method based on in-situ autogenous conductive particles, which is characterized by comprising the following steps:
step one, polydopamine modification treatment of polydimethylsiloxane prepolymer: putting the polydimethylsiloxane prepolymer into a tris hydrochloride buffer solution containing 1-20 g/L dopamine, stirring for 10-40 h under the condition that the pH value is 8.2-8.6, and generating polydopamine in the polydimethylsiloxane prepolymer through the polymerization reaction of the dopamine to obtain a polydopamine modified prepolymer;
step two, generating conductive particles in situ in the polydimethylsiloxane prepolymer: placing the polydopamine modified prepolymer obtained in the first step into an oven to dry residual moisture at low temperature, then adding a reducing agent solution containing metal ions for reduction reaction, generating conductive particles in situ in the prepolymer, and then performing ultrasonic dispersion in an ultrasonic cleaner for 120-240 min to obtain a prepolymer containing the conductive particles; the concentration of metal ions in the metal ion-containing reducing agent solution is 10g/L to 50g/L;
step three, solidifying and forming a polymer core mould: adding a curing agent into the prepolymer containing conductive particles obtained in the second step to form mixed slurry, pouring the mixed slurry on the surface of an original template with a microstructure on the surface until the microstructure is completely filled, placing the original template in a vacuum drying oven for degassing for 10-60 min, and then transferring the original template into an oven for low-temperature curing and forming to obtain a polymer core die conductive layer of which the microstructure on the surface is duplicated;
step four, micro electroforming of metal micro parts: performing insulation treatment on the back of the conductive layer of the polymer core mold obtained in the third step, punching holes on the upper end and the lower end of the core mold, penetrating into metal wires for fixation, immersing in micro electroforming solution to serve as a cathode for electrodeposition until metal ions are cast into the cavity of the polymer core mold, taking out the electrodeposited core mold, immersing in deionized water for ultrasonic cleaning, and drying in an oven to obtain the polymer core mold with the metal micro parts;
step five, demolding and post-treatment of the metal micro part: and D, taking out the metal micro part prepared in the fourth step from the cavity of the polymer core mold by adopting a manual demolding mode, and obtaining a metal micro part finished product through post-treatment.
According to the invention, the polydopamine is used for carrying out modification treatment on Polydimethylsiloxane (PDMS) prepolymer in a Tris (hydroxymethyl) aminomethane) (Tris) -HCl buffer solution, the phenolic hydroxyl and amino groups in polydopamine are used for improving the reactivity of the PDMS prepolymer, conductive particles are generated in situ in the PDMS prepolymer through the weak redox property of active groups and the complexing capacity of metal ions, and then a polymer core mold with excellent conductivity, high forming precision and reusability is prepared through casting forming and low-temperature curing treatment.
The polymer mandrel micro-electroforming method based on the in-situ autogenous conductive particles is characterized in that the conductive particles in the second step are Ag particles, cu particles or Ni particles. The invention comprehensively considers the factors such as cost, conductivity, preparation conditions and the like, and the conductive particles are common conductive particles for improving the conductivity of the polymer, so that the practicability of the invention is improved.
The polymer mandrel micro-electroforming method based on the in-situ autogenous conductive particles is characterized in that the volume of the curing agent in the mixed slurry in the step three is 10% -30% of the volume of the prepolymer containing the conductive particles. The invention can ensure the solidification and shaping of the core mould by controlling the volume content of the curing agent, and ensures that the core mould has excellent shaping precision and mechanical property.
One of the aboveThe polymer mandrel micro-electroforming forming method based on in-situ autogenous conductive particles is characterized in that the micro-electroforming liquid in the fourth step is a single metal solution, an alloy solution or a composite material solution, the electrodeposition comprises direct current deposition or pulse electrodeposition, and the current density is 1A/dm 2 ~20A/dm 2 . The invention is suitable for preparing metal micro parts of various materials, meets different use requirements, can ensure the timely discharge of hydrogen bubbles generated in the electrodeposition process by controlling the current density, and reduces pinhole defects in a casting layer.
The polymer mandrel micro-electroforming method based on the in-situ autogenous conductive particles is characterized in that the post-treatment in the fifth step comprises low-temperature heat treatment and surface polishing treatment. The invention improves the performance of the finished product of the metal micro part through post-treatment.
Compared with the prior art, the invention has the following advantages:
1. the conductive particles are generated in situ in the polymer matrix through the auxiliary reduction action of the polydopamine, so that the problems of complex preparation process, high cost and the like of the existing photoresist core mold are overcome, the micro electroforming core mold with high quality can be prepared at low cost, the damage of the demolding process to the core mold microstructure can be reduced due to the excellent elasticity and toughness of the polymer core mold, and the core mold can be reused after being cleaned.
2. The invention generates conductive particles in situ in the polymer matrix, not only endows the micro electroforming mandrel with excellent conductivity and forming precision, but also maintains the elasticity and toughness of the polymer, reduces the damage of the demoulding process to the microstructure of the mandrel, prolongs the service life of the mandrel, and solves the problem that the existing photoresist mandrel can only be used once.
3. The invention realizes the uniform dispersion of the conductive particles in the polymer core mold by generating the conductive particles in situ in the polymer matrix, avoids the uneven distribution of the power lines caused by the aggregation of the conductive particles, and improves the forming precision of the metal micro parts.
4. The polymer core mould can be reused, so that the preparation cost is reduced, and the resources are saved.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is a schematic structural diagram of a polydimethylsiloxane prepolymer of the invention.
FIG. 2 is a schematic structural diagram of a polydopamine modified prepolymer of the present invention.
FIG. 3 is a schematic structural view of a prepolymer containing conductive particles according to the present invention.
FIG. 4 is a schematic diagram of the connection between the original template and the conductive layer of the polymer mandrel according to the present invention.
Fig. 5 is a schematic diagram of the connection between the insulating layer of the polymer core and the conductive layer of the polymer core according to the present invention.
Fig. 6 is a schematic diagram of the connection between the original form and the polymer core according to the present invention.
Fig. 7 is a schematic structural view of a polymer core according to the present invention.
Fig. 8 is a schematic diagram of the connection between a polymer core and a metal wire according to the present invention.
FIG. 9 is a schematic diagram of the micro-electroforming of the present invention.
Fig. 10 is a schematic diagram of the connection between a metal micro part and a polymer core mold according to the present invention.
FIG. 11 is a morphology diagram of a nickel micro part prepared in example 1 of the present invention.
FIG. 12 is a morphology diagram of a miniature nickel-iron alloy part prepared in example 2 of the present invention.
FIG. 13 is a morphology diagram of a micro part of the nickel iron/aluminum oxide composite material prepared in example 3 of the present invention.
Reference numerals illustrate:
1-polydimethylsiloxane prepolymer; 2-polydopamine modified pre-polymer;
3-a prepolymer containing conductive particles; 4-original template; 5-a polymeric mandrel conductive layer;
6-a polymer mandrel insulating layer; 7-a polymer core; 8-metal wire; 9-metal ions;
10-metal micro parts.
Detailed Description
FIG. 1 is a schematic structure diagram of a polydimethylsiloxane prepolymer of the present invention, FIG. 2 is a schematic structure diagram of a polydopamine-modified prepolymer of the present invention, FIG. 3 is a schematic structure diagram of a prepolymer containing conductive particles of the present invention, FIG. 4 is a schematic connection diagram of an original mold plate and a conductive layer of a polymer core mold of the present invention, FIG. 5 is a schematic connection diagram of an insulating layer of a polymer core mold and a conductive layer of a polymer core mold of the present invention, FIG. 6 is a schematic connection diagram of an original mold plate and a polymer core mold of the present invention, FIG. 7 is a schematic structure diagram of a polymer core mold of the present invention, FIG. 8 is a schematic connection diagram of a polymer core mold and a metal wire of the present invention, FIG. 9 is a schematic connection diagram of a micro-metal part of the present invention and a polymer core mold of the present invention, as can be seen from fig. 1 to 10, according to the present invention, a polydimethylsiloxane prepolymer 1 is treated to obtain a polydopamine modified prepolymer 2, conductive particles are generated in situ in the polydopamine modified prepolymer 2 to obtain a prepolymer 3 containing conductive particles, the prepolymer 3 containing conductive particles is poured on the surface of an original template 4 with a microstructure until the microstructure is completely filled, a polymer core mold conductive layer 5 is obtained on the original template 4, a polymer core mold insulating layer 6 is prepared on the polymer core mold conductive layer 5 to obtain a polymer core mold 7, the upper end and the lower end of the polymer core mold 7 are perforated and penetrated into a metal wire 8 to be fixed, electrodeposition is performed as a cathode, after metal ions 9 are deposited and cast into the cavity of the polymer core mold 7, and demolding is performed to obtain a metal micro part 10.
Example 1
The embodiment comprises the following steps:
step one, polydopamine modification treatment of PDMS prepolymer: 180mL of aqueous solution containing 1.2g of Tris is added into 20mL of PDMS prepolymer, diluted hydrochloric acid is added dropwise to adjust the pH of the mixed solution to 8.2, then 0.2g of dopamine is added and stirred for 10 hours at room temperature, polydopamine is generated in the PDMS prepolymer through polymerization reaction of the dopamine, and the polydopamine modified PDMS prepolymer is obtained;
step two, generating conductive particles in situ in the PDMS prepolymer: putting the polydopamine modified PDMS prepolymer obtained in the first step into a baking oven at 50 ℃ to dry residual moisture, then adding silver ammonia-glucose solution as a reducing agent to react for 40 minutes at room temperature, catalyzing silver ions in the solution by active groups in polydopamine to perform reduction reaction to generate conductive silver particles in situ in the PDMS prepolymer, and performing ultrasonic treatment in an ultrasonic cleaner for 120 minutes to uniformly disperse the silver particles in the PDMS prepolymer to obtain the PDMS prepolymer containing the conductive particles; the preparation process of the silver ammonia-glucose solution comprises the following steps: dissolving 10g of silver nitrate into 1L of deionized water, slowly dropwise adding ammonia water until the solution becomes turbid from clarification, stopping dropwise adding ammonia water when the solution becomes colorless and transparent from turbidity to obtain a silver ammonia solution, adding 10g of glucose, mixing and stirring at room temperature for 30min to obtain a silver ammonia-glucose solution;
step three, solidifying and forming a polymer core mould: adding 2mL of Dow Corning 184 curing agent into the PDMS prepolymer containing conductive particles obtained in the second step to form mixed slurry, then pouring the mixed slurry on the surface of an original template with a microstructure on the surface until the microstructure is completely filled, placing the mixed slurry in a vacuum drying oven to remove gas for 10min, then transferring the mixed slurry into the oven to be cured and formed at 150 ℃ for 180min, and copying and forming a polymer core die conductive layer on the surface of the original template; a plurality of micro-channel structures with the width of 160 mu m are uniformly etched on the surface of the original template;
step four, micro electroforming of the nickel micro part: pouring insulating silica gel slurry prepared by uniformly mixing 5mL of PDMS prepolymer and 0.5mL of Conning 184 curing agent on the back of the conductive layer of the polymer core mold obtained in the step three, placing the insulating silica gel slurry in an oven, curing and forming for 30min at a low temperature of 100 ℃ to obtain the insulating layer of the polymer core mold, insulating the back of the core mold to obtain the polymer core mold, punching holes at the upper end and the lower end of the polymer core mold, penetrating metal wires for fixing, immersing the polymer core mold into micro electroforming liquid to serve as a cathode for electro-deposition, selecting a pure nickel sheet as an anode, performing micro electroforming by adopting pulse current through an electrochemical workstation, taking out the electro-deposited core mold, immersing the electro-deposited core mold into deionized water for ultrasonic cleaning, and drying in the oven to obtain the polymer core mold with nickel micro parts; the micro-electroforming solution comprises the following components: 300g/L nickel sulfate, 50g/L boric acid and nickel chloride50g/L, 1g/L sodium dodecyl sulfonate and 15g/L saccharin; the pH value of the micro-electroforming solution is adjusted to 3.5 by adopting a dilute sulfuric acid solution; the temperature of the pulse current for micro-electroforming is 55 ℃, and the current density is 1A/dm 2 ；
Step five, demolding and post-treatment of the nickel micro part: and (3) taking the nickel micro part prepared in the fourth step out of the cavity of the polymer core mold by adopting a manual demolding mode, carrying out annealing treatment at 300 ℃, surface polishing and other post-treatments to obtain a required nickel micro part finished product, and ultrasonically cleaning the demolded polymer core mold in deionized water for reuse.
Fig. 11 is a morphology diagram of the nickel micro part prepared in the present embodiment, and as can be seen from fig. 11, the nickel micro part micro electroformed in the present embodiment has a complete defect-free structure, and completely replicates the microstructure of the original template, which illustrates that the single metal micro part prepared by the method of the present invention has excellent replication forming precision.
Example 2
The embodiment comprises the following steps:
step one, polydopamine modification treatment of PDMS prepolymer: 180mL of an aqueous solution containing 1.2g of Tris is added into 20mL of PDMS prepolymer, diluted hydrochloric acid is added dropwise to adjust the pH of the mixed solution to 8.5, 2g of dopamine is added and stirred for 20h at room temperature, and polydopamine is generated in the PDMS prepolymer through the polymerization reaction of the dopamine, so that the polydopamine modified PDMS prepolymer is obtained.
Step two, generating conductive particles in situ in the PDMS prepolymer: putting the polydopamine modified PDMS prepolymer obtained in the first step into a baking oven at 50 ℃ to dry residual moisture, then adding an electroless copper plating solution as a reducing agent to react for 40 minutes at room temperature, catalyzing copper ions in the solution by active groups in polydopamine to perform reduction reaction to generate conductive copper particles in situ in the PDMS prepolymer, and performing ultrasonic treatment in an ultrasonic cleaner for 180 minutes to uniformly disperse the copper particles in the PDMS prepolymer to obtain the PDMS prepolymer containing the conductive particles; the electroless copper plating solution contains the following components: 60g/L of potassium sodium tartrate, 30g/L of copper sulfate, 3g/L of sodium borohydride and 30g/L of sodium hydroxide; the pH value of the electroless copper plating solution is adjusted to 13.0 by a dilute sulfuric acid solution;
step three, solidifying and forming a polymer core mould: adding 4mL of Dow Corning 184 curing agent into the PDMS prepolymer containing the conductive particles obtained in the second step to form mixed slurry, then pouring the mixed slurry on the surface of an original template with a microstructure on the surface until the microstructure is completely filled, placing the mixed slurry in a vacuum drying oven to remove gas for 30min, then transferring the mixed slurry into the oven to be cured and formed at 150 ℃ for 180min, and copying and forming a polymer core die conductive layer on the surface of the original template; a plurality of micro-channel structures with the width of 120 mu m are uniformly etched on the surface of the original template;
step four, micro electroforming forming of the ferronickel miniature part: pouring insulating silica gel slurry prepared by uniformly mixing 5mL of PDMS prepolymer and 0.5mL of Conning 184 curing agent on the back of the conductive layer of the polymer core mold obtained in the step three, placing the insulating silica gel slurry in an oven, curing and forming for 30min at a low temperature of 100 ℃ to obtain the insulating layer of the polymer core mold, insulating the back of the core mold to obtain the polymer core mold, punching holes at the upper end and the lower end of the polymer core mold, penetrating metal wires for fixing, immersing the polymer core mold into micro electroforming liquid as a cathode for electro-deposition, adopting a nickel sheet and iron sheet combination with an area ratio of 3:1 for micro-electroforming by an electrochemical workstation, taking out the electro-deposited core mold, immersing the core mold in deionized water for ultrasonic cleaning, and drying in the oven to obtain the polymer core mold with the micro nickel-iron alloy part; the micro-electroforming solution comprises the following components: 300g/L of nickel sulfate, 100g/L of ferrous sulfate, 50g/L of boric acid, 50g/L of nickel chloride, 1.5g/L of sodium dodecyl sulfate, 20g/L of saccharin, 5g/L of glucose, 3g/L of ascorbic acid, 3g/L of glycine and 2g/L of sodium gluconate; the pH value of the micro-electroforming solution is adjusted to 5.5 by adopting a dilute sulfuric acid solution; the temperature of the direct current for micro electroforming is 55 ℃, and the current density is 10A/dm 2 ；
Step five, demoulding and post-treatment of the ferronickel miniature part: and (3) taking the ferronickel micro part prepared in the step four out of the cavity of the polymer core mold by adopting a manual demolding mode, and carrying out post-treatment such as annealing treatment at 300 ℃ and surface polishing to obtain the required ferronickel micro part, wherein the polymer core mold after demolding is ultrasonically cleaned in deionized water for reuse.
Fig. 12 is a morphology diagram of the ferronickel micro part prepared in the present embodiment, and as can be seen from fig. 12, the ferronickel micro part prepared in the present embodiment has a complete structure without defects, and a complete microstructure of the original template is duplicated, which illustrates that the alloy micro part prepared by the method of the present invention has excellent duplication forming precision.
Example 3
The embodiment comprises the following steps:
step one, polydopamine modification treatment of PDMS prepolymer: 180mL of aqueous solution containing 1.2g of Tris is added into 20mL of PDMS prepolymer, diluted hydrochloric acid is added dropwise to adjust the pH of the mixed solution to 8.6, then 4g of dopamine is added and stirred for 20h at room temperature, and polydopamine is generated in the PDMS prepolymer through the polymerization reaction of the dopamine, so that polydopamine modified PDMS prepolymer is obtained;
step two, generating conductive particles in situ in the PDMS prepolymer: putting the polydopamine modified PDMS prepolymer in the first step into a baking oven at 50 ℃ to dry residual moisture, then adding a chemical nickel plating solution to react for 40min at room temperature, performing reduction reaction on nickel ions in the active group catalytic solution in polydopamine to generate conductive nickel particles in situ in the PDMS prepolymer, and then performing ultrasonic treatment in an ultrasonic cleaner for 240min to uniformly disperse the nickel particles in the PDMS prepolymer to obtain the PDMS prepolymer containing the conductive particles; the electroless nickel plating solution comprises the following components: 50g/L of nickel chloride, 25g/L of sodium citrate, 20g/L of sodium hypophosphite and 10g/L of sodium acetate, wherein the pH value of the electroless nickel plating solution is adjusted to 5.0 by a dilute hydrochloric acid solution;
step three, solidifying and forming a polymer core mould: adding 6mL of Dow Corning 184 curing agent into the PDMS prepolymer containing the conductive particles obtained in the second step to form mixed slurry, then pouring the mixed slurry on the surface of an original template with a microstructure on the surface until the microstructure is completely filled, placing the mixed slurry in a vacuum drying oven to remove gas for 60min, then transferring the mixed slurry into the oven to be cured and formed at 150 ℃ for 180min, and copying and forming a polymer core die conductive layer on the surface of the original template; a plurality of micro-channel structures with the width of 20 mu m are uniformly etched on the surface of the original template;
step four, micro electroforming forming of the nickel-iron/aluminum oxide composite material micro part: pouring insulating silica gel slurry prepared by uniformly mixing 5mL of PDMS prepolymer and 0.5mL of Conning 184 curing agent on the back of the conductive layer of the polymer core mold, placing the insulating silica gel slurry in an oven, curing and forming for 30min at a low temperature of 100 ℃ to obtain the insulating layer of the polymer core mold, insulating the back of the core mold to obtain the polymer core mold, punching holes at the upper end and the lower end of the polymer core mold, penetrating metal wires 8 into the polymer core mold for fixing, immersing the polymer core mold into an alumina-containing micro electroforming solution to serve as a cathode for electro-deposition, combining a nickel sheet and an iron sheet with an area ratio of 3:1, performing micro-electroforming by adopting direct current through an electrochemical workstation, taking out the electro-deposited core mold, immersing the electro-deposited core mold into deionized water for ultrasonic cleaning, and placing the polymer core mold in the oven for drying to obtain the polymer core mold with the micro-sized part of the nickel-iron/alumina composite material;
the alumina-containing micro-electroforming solution contains the following components: 300g/L of nickel sulfate, 100g/L of ferrous sulfate, 50g/L of boric acid, 50g/L of nickel chloride, 1.5g/L of sodium dodecyl sulfate, 20g/L of saccharin, 5g/L of glucose, 3g/L of ascorbic acid, 3g/L of glycine, 2g/L of sodium gluconate and 20g/L of alumina powder with the average particle size of 0.3 mu m; the pH value of the alumina-containing micro-electroforming solution is adjusted to 5.5 by adopting a dilute sulfuric acid solution; the temperature of the direct current for micro electroforming is 50 ℃, and the current density is 20A/dm 2 ；
Step five, demoulding and post-treatment of the ferronickel/aluminum oxide composite material micro part: and (3) taking the miniature part of the nickel-iron/aluminum oxide composite material prepared in the step (IV) out of the cavity of the polymer core mold by adopting a manual demolding mode, and carrying out annealing treatment at 400 ℃, surface polishing and other post-treatment to obtain the required miniature part of the nickel-iron/aluminum oxide composite material, wherein the polymer core mold after demolding is ultrasonically cleaned in deionized water for reuse.
Fig. 13 is a morphology diagram of the nickel-iron/aluminum oxide composite micro part prepared in the present embodiment, and as can be seen from fig. 13, the micro electroformed nickel-iron/aluminum oxide composite micro part in the present embodiment has a complete and defect-free structure, and completely replicates the microstructure of the original template, which illustrates that the composite micro part prepared by the method of the present invention has excellent replication forming precision.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (5)
1. A polymer mandrel micro-electroforming method based on in-situ autogenous conductive particles, which is characterized by comprising the following steps:
step one, polydopamine modification treatment of polydimethylsiloxane prepolymer: putting the polydimethylsiloxane prepolymer into a tris hydrochloride buffer solution containing 1-20 g/L dopamine, stirring for 10-40 h under the condition that the pH value is 8.2-8.6, and generating polydopamine in the polydimethylsiloxane prepolymer through the polymerization reaction of the dopamine to obtain a polydopamine modified prepolymer;
step two, generating conductive particles in situ in the polydimethylsiloxane prepolymer: placing the polydopamine modified prepolymer obtained in the first step into an oven to dry residual moisture at low temperature, then adding a reducing agent solution containing metal ions for reduction reaction, generating conductive particles in situ in the prepolymer, and then performing ultrasonic dispersion in an ultrasonic cleaner for 120-240 min to obtain a prepolymer containing the conductive particles; the concentration of metal ions in the metal ion-containing reducing agent solution is 10g/L to 50g/L;
step three, solidifying and forming a polymer core mould: adding a curing agent into the prepolymer containing conductive particles obtained in the second step to form mixed slurry, pouring the mixed slurry on the surface of an original template with a microstructure on the surface until the microstructure is completely filled, placing the original template in a vacuum drying oven for degassing for 10-60 min, and then transferring the original template into an oven for low-temperature curing and forming to obtain a polymer core die conductive layer of which the microstructure on the surface is duplicated;
step four, micro electroforming of metal micro parts: performing insulation treatment on the back of the conductive layer of the polymer core mold obtained in the third step, punching holes on the upper end and the lower end of the core mold, penetrating into metal wires for fixation, immersing in micro electroforming solution to serve as a cathode for electrodeposition until metal ions are cast into the cavity of the polymer core mold, taking out the electrodeposited core mold, immersing in deionized water for ultrasonic cleaning, and drying in an oven to obtain the polymer core mold with the metal micro parts;
step five, demolding and post-treatment of the metal micro part: and D, taking out the metal micro part prepared in the fourth step from the cavity of the polymer core mold by adopting a manual demolding mode, and obtaining a metal micro part finished product through post-treatment.
2. The method of in-situ self-generating conductive particle based polymer mandrel micro-electroforming according to claim 1, wherein in the second step, the conductive particles are Ag particles, cu particles or Ni particles.
3. The method for micro-electroforming a polymer mandrel based on in-situ self-generated conductive particles according to claim 1, wherein the volume of the curing agent in the mixed slurry in the third step is 10% -30% of the volume of the prepolymer containing the conductive particles.
4. The method for micro-electroforming a polymer mandrel based on in-situ self-generated conductive particles according to claim 1, wherein in the fourth step, the micro-electroforming solution is a single metal solution, an alloy solution or a composite material solution, and the electrodeposition comprises direct current deposition or pulse electrodeposition, and the current density is 1A/dm 2 ~20A/dm 2 。
5. A polymer mandrel micro-electroforming process based on in-situ autogenous conductive particles according to claim 1, wherein the post-treatment in step five comprises a low temperature heat treatment and a surface polishing treatment.
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