CN113073363A - Chemical bonding method suitable for endoscope structure - Google Patents
Chemical bonding method suitable for endoscope structure Download PDFInfo
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- CN113073363A CN113073363A CN202110300217.4A CN202110300217A CN113073363A CN 113073363 A CN113073363 A CN 113073363A CN 202110300217 A CN202110300217 A CN 202110300217A CN 113073363 A CN113073363 A CN 113073363A
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- joint surface
- layer
- microstructure array
- bonding
- joint
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- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000000126 substance Substances 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 34
- 238000000576 coating method Methods 0.000 claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- 238000007747 plating Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000005530 etching Methods 0.000 claims abstract description 20
- 239000003792 electrolyte Substances 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 239000007769 metal material Substances 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 230000009916 joint effect Effects 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 230000003197 catalytic effect Effects 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 230000007797 corrosion Effects 0.000 claims description 10
- 238000005260 corrosion Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 8
- 238000006073 displacement reaction Methods 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000004471 Glycine Substances 0.000 claims description 6
- 150000004696 coordination complex Chemical class 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000009713 electroplating Methods 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 238000004381 surface treatment Methods 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 4
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 235000018417 cysteine Nutrition 0.000 claims description 3
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001453 nickel ion Inorganic materials 0.000 claims description 3
- 239000002861 polymer material Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000001039 wet etching Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 2
- 239000004475 Arginine Substances 0.000 claims description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 2
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001430 chromium ion Inorganic materials 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000010408 film Substances 0.000 description 11
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 8
- 239000008213 purified water Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 235000001014 amino acid Nutrition 0.000 description 5
- 150000001413 amino acids Chemical class 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000010355 oscillation Effects 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000006399 behavior Effects 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
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- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005323 electroforming Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000752 ionisation method Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 238000010023 transfer printing Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- LYFDUQMGDPBGMQ-DKWTVANSSA-N (2s)-2-amino-3-hydroxypropanoic acid;copper Chemical compound [Cu].OC[C@H](N)C(O)=O LYFDUQMGDPBGMQ-DKWTVANSSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- VVYPIVJZLVJPGU-UHFFFAOYSA-L copper;2-aminoacetate Chemical compound [Cu+2].NCC([O-])=O.NCC([O-])=O VVYPIVJZLVJPGU-UHFFFAOYSA-L 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
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- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- -1 platinum ions Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000001291 vacuum drying Methods 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
- C25D1/06—Wholly-metallic mirrors
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses a chemical bonding method suitable for an endoscope structure, which comprises the steps of pretreating a bonding surface of heterogeneous materials to be bonded to expose the materials of the bonding surface; etching the exposed joint surface to generate a microstructure array pattern in dense arrangement on the surface; then, manufacturing nano-scale micropores on the surface of the pattern; respectively carrying out replacement layer growth, seed crystal layer replacement and middle layer plating on the microstructure array pattern of the heterogeneous material to be jointed in sequence to obtain a composite plating layer; the materials to be jointed are respectively connected with the anode and the cathode, ion sources are supplemented through electrolyte under the action of high-voltage current, the composite coating generates transfer ion reaction, and a continuous surface joint surface is directly formed on the joint surface to achieve the joint effect. The composite coating of the invention can be suitable for the growth of the crystal face of the corresponding metal material in the exchange process of surface charge through wet electrochemical bonding, and then an effective bonding state is generated, and the effective bonding and embedding of two heterogeneous materials are achieved.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a chemical bonding method suitable for an endoscope structure.
Background
In the aspect of medical related fields, regarding the medical behaviors and applications of medical instruments which are most suitable for the public, under the rapid development state of medical instruments, especially the invasive endoscope and other related technologies are most commonly used in various types of surgical operations or related medical behaviors, however, various endoscopes in medical instruments need to be adapted to the consideration of the harsh external physiological environment factors formed by the acid-base environment and the related physiological environment in the human body, so that establishing a tabling joint assembly technology which can form a high-safety endoscope is an important issue and a deeply-researched field in the field of endoscope assembly.
In various types of endoscope structure products, particularly those used in medical treatment, it is necessary to deal with severe environmental factors, such as physiological environment, acid-base environment, and bacterial environment, which may cause corrosion or potential structural damage to the endoscope structure and the related joint surface due to unexpected damage.
Disclosure of Invention
The invention aims to provide a chemical bonding method suitable for endoscope structure heterogeneous materials, which can effectively overcome the limitation of external conditions such as various material characteristics, package shapes and the like, and completely resist the defects of incomplete package caused by corrosion behavior and related structural destruction behavior.
In order to achieve the purpose, the technical scheme is as follows:
a method of chemical bonding suitable for use with an endoscopic structure, comprising the steps of:
(1) surface treatment
Pretreating the joint surface of the heterogeneous materials to be jointed to expose the materials of the joint surface;
(2) microstructure array preparation
Etching the exposed joint surface to generate a microstructure array pattern in dense arrangement on the surface; then, manufacturing nano-scale micropores on the surface of the pattern;
(3) preparation of composite coating
Respectively carrying out replacement layer growth, seed crystal layer replacement and middle layer plating on the microstructure array pattern of the heterogeneous material to be jointed in sequence to obtain a composite plating layer;
(4) wet electrochemical bonding
The materials to be jointed are respectively connected with the anode and the cathode, ion sources are supplemented through electrolyte under the action of high-voltage current, the composite coating generates transfer ion reaction, and a continuous surface joint surface is directly formed on the joint surface to achieve the joint effect.
According to the scheme, the heterogeneous material comprises a metal material, a semiconductor material or a high polymer material.
According to the scheme, the surface treatment process in the step 1 comprises corrosion or cleaning or corrosion plus cleaning.
According to the scheme, the microstructure array preparation in the step 2 adopts a wet etching and impressing array pattern, and the specific process is as follows:
preparing a mold with a microstructure array, carrying out catalytic corrosion by using an electrolytic reaction suitable for a joint surface material, and reversely etching and copying a microstructure array pattern of the mold on a joint surface.
According to the scheme, the preparation of the microstructure array in the step 2 adopts a dry-type imprinting and transfer printing array pattern, and the specific process is as follows:
preparing a mold with a microstructure array, and forming a microstructure array pattern of the mold on a joint surface by dry electrolytic imprinting suitable for the joint surface material.
According to the scheme, the replacement layer in the step 3 grows, and the method comprises the following steps:
immersing the joint surface into catalytic electrolytic metal complex solution to enable the metal complex to form a catalytic ion layer on the surface of the microstructure array; the complex liquid is a complex solution of tin dioxide and glycine, cysteine, arginine or serine.
According to the scheme, the seed layer replacement in the step 3 comprises the following steps:
and soaking the joint surface into chloride solution of gold, silver, palladium or platinum, and performing displacement under the catalysis of the catalytic ion layer, so that the catalytic ion layer on the surface of the microstructure array absorbs and displaces to form a metal coating.
According to the scheme, the intermediate layer plating layer in the step 3 comprises the following steps:
and electroplating nickel, copper, zinc, chromium or titanium on the metal coating on the surface of the microstructure array through three electrodes to obtain an intermediate coating.
According to the scheme, the electrolyte in the step 4 mainly comprises a nickel ion source and contains nickel sulfate/nickel chloride/hydrochloric acid/additives; wherein the nickel sulfate is 0.5-1M; 0.5-1M of nickel chloride; 0.1-0.2M of hydrochloric acid; the additive is glycine, polyvinyl alcohol or glacial acetic acid.
According to the scheme, the electrolyte in the step 4 mainly comprises a chromium ion source and contains chromium sulfate/chromium chloride/hydrochloric acid/sulfuric acid/additives; wherein the chromium sulfate is 0.5-1M; 0.5-1M of chromium chloride; adding 0.1-0.2M of sulfuric acid into hydrochloric acid; the additive is glycine, polyvinyl alcohol or glacial acetic acid. M (mol/L).
Compared with the prior art, the beneficial effects are as follows:
the heterogeneous material bonding method can be directly used for surface bonding of heterogeneous special-shaped structures, and the structural shapes of the heterogeneous material bonding method are not limited to circular, annular, square or related specific shapes; is particularly suitable for assembling and manufacturing the endoscope structure.
The composite coating is jointed through wet electrochemical process, and the surface charge exchange process is suitable for the corresponding crystal surface growth process of metal material to generate ionization process, so that the ionization process and the carrier redistribution process of the material are generated, and an effective jointing state is generated, and the effective jointing and embedding of two heterogeneous materials are realized. The two-phase fluid fusion process similar to instantaneous jointing is produced, the compact structure representation of jointing embedding is effectively formed, and the method can be effectively applied to the jointing process of metal materials.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but should not be construed as limiting the scope of the present invention.
For example, the endoscope structure is chemically bonded, and the common embodiments mostly relate to stainless steel and glass or related polymer materials, such as indium tin oxide glass, fluorinated glass, sapphire glass, and plastic lens.
(1) And removing the original film layer, namely performing surface treatment.
The process is mainly used for removing a workpiece surface layer material needing plating treatment, such as a thin film with a protective effect on the surface of a metal or alloy material, and any corrosion, etching or plating treatment needs to be carried out by removing the film first so as to be beneficial to the execution of subsequent actions.
Taking stainless steel alloy as an example, a chromized film which is easy to be oxidized is generated on the surface due to the components of iron, nickel, gold and chromium metal, before cleaning and corrosion are carried out to a certain depth, a chromium oxide film is continuously generated for protection, and the film needs to be effectively removed through the action of corrosion, so that the subsequent process is facilitated.
(2) And (4) preparing a microstructure.
The process action is mainly to prepare a surface microstructure on the joint surface of a workpiece to be jointed after the original film layer is removed or the original film layer is not required to be removed, wherein the microstructure can be prepared by adopting wet-type impression etching or dry-type impression transfer printing, so that a densely arranged ordered array pattern is generated on the surface of the microstructure, and the subsequent process of treating a coating can be facilitated to coat the coating on the surface of the pattern according to the basic shape of the pattern.
Wet etching imprint patterning: by utilizing the micro-structure array which is precisely processed, an electrolytic reaction which is suitable for the materials of the workpieces to be jointed and can carry out catalytic corrosion is formulated, the pattern of the precise die can be directly reversely etched and copied on the joint surface of the workpieces to be jointed, and the array micro-structure pattern to be formed can be formed.
The specific operation is as follows:
1. an ultra-precise mold is adopted, the pyramid structure of the mold is 0.1-0.3um, the interval is 0.05-0.1um, and the mold is made of high-rigidity materials such as stainless steel, silicon base, tungsten steel and the like;
2. preparing special etching liquid, and preparing hydrofluoric acid, hydrogen peroxide, isopropanol and water in a ratio of 1:5:0.5: 10;
3. forming an electrochemical etching reaction, and configuring an electrode (mold) for etching, a carbon electrode (processing workpiece) and a reference electrode;
4. carrying out wet micro-nano imprinting, keeping pressure between the workpiece and the mold, and conducting current to form electrochemical etching reaction;
5. adjusting voltage to 0.01-1.37-2.0V and 0.05-0.1A, observing potential output to a descending trend with reference to an electrochemical workstation, wherein the operation time can be 0-60 seconds;
6. after the reaction, the reaction solution is washed, and ultrasonic oscillation washing is sequentially carried out for 1 minute, 1 minute and 5 minutes by using purified water/IPA/purified water, and then drying is carried out.
Dry imprint transfer: the micro-structure array is precisely processed, the joint surface of the workpieces to be jointed is impacted by electrolysis to form a two-phase interface capable of being dissolved and diffused temporarily, and the array micro-structure pattern is formed on the joint surface by dry electrolytic imprinting. Or the micro-structure array which is precisely processed is used for making imprinting which is suitable for the materials of the workpieces to be jointed and can carry out thermoplastic physical contact surface softening and solidification, and the pattern of the precise mould can be directly reversely etched and copied on the jointing surface of the workpieces to be jointed, so that the array micro-structure pattern to be formed can be formed.
The specific operation is as follows:
1. an ultra-precise mold is adopted, the pyramid structure of the mold is 0.1-0.3um, the interval is 0.05-0.1um, and the mold is made of high-rigidity materials such as stainless steel, silicon base, tungsten steel and the like;
2. cleaning a mould, preparing isopropanol, cleaning for 1 minute by ultrasonic oscillation, and cleaning for 1 minute by ultrasonic oscillation with ultrapure water;
3. carrying out vacuum drying on the mold to ensure that no residue is left after removing surface moisture;
4. heating the mould for reaction, and configuring and maintaining the temperature in the range of 5-10 ℃ greater than the melting point of the material to be imprinted;
5. carrying out dry-method micro-nano imprinting, keeping pressure between the workpiece and the mold, and heating to form a thermoplastic imprinting reaction;
6. adjusting the temperature and holding the temperature for 10-30 seconds, and then cooling, curing and shaping, wherein the operation time can be 300 seconds;
7. after the reaction, the reaction solution is washed, and ultrasonic oscillation washing is sequentially carried out for 1 minute, 1 minute and 5 minutes by using purified water/IPA/purified water, and then drying is carried out.
The second surface micro-etching mainly acts on the workpiece which is subjected to patterning growth, and the preparation of the nano-scale micropores is carried out:
1. preparing special etching liquid, and preparing hydrofluoric acid, hydrogen peroxide, isopropanol, chloroplatinic acid and water in a ratio of 1:5:0.5:0.1: 10;
2. the area of the workpiece which does not need to be etched is completely sealed and coated, so that liquid impermeability is ensured;
3. forming an electrochemical etching reaction, and configuring an electrode (processing workpiece) for etching, a carbon electrode and a reference electrode;
4. carrying out wet-process nanopore etching, soaking the workpiece in etching liquid, and conducting current to form electrochemical etching reaction;
5. adjusting voltage to 0.01-1.37-2.0V and 0.05-0.1A, observing potential output to a descending trend with reference to an electrochemical workstation, wherein the operation time can be 0-10 seconds;
6. after the reaction, the reaction solution is washed, and ultrasonic oscillation washing is sequentially carried out for 1 minute, 1 minute and 5 minutes by using purified water/IPA/purified water, and then drying is carried out.
(3) And (4) preparing a composite coating.
The process is used for coating the prepared microstructure array of the workpiece to be jointed so as to facilitate the subsequent heterogeneous jointing, and the composite coating needs to be sequentially subjected to three steps.
Growing a replacement layer: after the prepared microstructure array of the workpieces to be jointed is cleaned, an active catalytic electrolysis metal complex solution, which is usually a complex solution of tin dioxide and specific amino acid, is put into the microstructure array of the workpieces, so that the microstructure array of the workpieces is immersed in the liquid, and the metal complex (such as copper glycine complex Cu-Gly, copper serine complex Cu-Ser and copper cysteine complex Cu-Cys) can form an active catalytic ion layer on the surface of the microstructure array.
The specific operation is as follows:
1. ultrasonically cleaning the workpiece with the surface hardening film removed in purified water for 5 minutes to ensure that the microstructure array is clean;
2. placing the mixture into an IPA cleaning solution ultrasonic cleaning tank for cleaning for 5 minutes to ensure that organic matters are removed;
3. cleaning in a purified water ultrasonic cleaning tank for 5 min to ensure removal of IPA;
4. with tin dioxide SnCl2And preparing 0.1M solution by using dilute hydrochloric acid and amino acid, and soaking the workpiece microstructure array in the solution for 1 minute to ensure that the surface of the workpiece is filled with tin ions to obtain the catalytic ion layer.
Seed layer replacement: the microstructure array for growing the replacement layer is immersed in chloride solution containing noble metal such as gold, silver, palladium, platinum and the like, so that metal source ions of the type are replaced by catalysis of a catalytic ion layer, and are directly adsorbed and replaced by a pure metal plating layer on the surface, wherein the plating layer usually selects a crystal phase matched with the next step, and the seed crystal layer is mainly selected to correspond to a metal film to be coated and has a substrate layer capable of catalyzing the plating film, so that effective plating layer joint force and catalytic growth effects are generated.
The specific operation is as follows:
1. taking a platinum coating as a case, preparing 0.1M solution by chloroplatinic acid diluted hydrochloric acid;
2. placing the replacement layer on the surface of the microstructure array of the workpiece into the displacement layer for displacement reaction, wherein Sn ions on the surface of the workpiece and platinum ions generate displacement reduction reaction, and a platinum metal coating is directly formed on the surface;
3. ensuring that the stable plating layer can adopt the subsequent platinum electroplating process;
4. preparing 0.1N-0.5N chloroplatinic acid/dilute hydrochloric acid/water electrolyte;
5. a plating electrode (workpiece), a carbon electrode and a reference electrode are configured;
6. adjusting the voltage to 0.01-1.10V and 0.05-0.1A, referring to the electrochemical workstation, and observing the potential output to a descending trend to complete the platinum coating process. The plating process can be selected from evaporation or sputtering.
And (3) intermediate layer plating: after the metal plating layer such as gold, silver, palladium, platinum and the like is finished, the plating film generation process of the middle layer is carried out. The selection of the plating layer can be generally selected to be matched with the crystal phase selection of a bonding layer of a seed crystal layer and a next layer, and the selection of the following related metal ion sources such as nickel, copper, zinc, chromium, titanium and the like is generally selected based on the selection of strength, rigidity and toughness, and the plating reaction can directly utilize pure electroplating reaction. The method comprises the steps of configuring a three-phase electrode, a cathode, an anode and a reference electrode, configuring an electrolyte containing a metal source, configuring one electrode as a workpiece to be clamped, configuring the other electrode as a carbon electrode, selecting an electrochemical oxidation-reduction potential suitable for a coating as a basic voltage, adjusting proper current input, performing staged coating of the coating, improving input of adjusting current when the coating is nearly finished, stabilizing the strength and the bonding force of the coating, and then performing slow adjusting current to control the quality of the coating.
The preparation process comprises the following steps:
1. taking a platinum coating as a case, preparing 0.1-0.5M solution by nickel nitrate, chromium nitrate, dilute hydrochloric acid and dilute nitric acid;
2. placing a workpiece into the reaction vessel for a displacement reaction, wherein a noble metal layer such as platinum on the surface of the workpiece and nickel ions generate a displacement reduction reaction, and a nickel metal coating is directly formed on the surface;
3. ensuring that the stable plating layer can adopt the subsequent nickel electroplating process;
4. preparing 0.1N-0.5N of nickel nitrate/chromium nitrate/dilute hydrochloric acid/amino acid/water electrolyte;
5. a plating electrode (workpiece), a carbon electrode and a reference electrode are configured;
6. adjusting the voltage to 0.01-1.10V and 0.05-0.1A, referring to the electrochemical workstation, and observing the potential output to a descending trend to complete the platinum coating process.
(4) Wet electrochemical bonding.
Preparing electrolyte from nickel nitrate, chromium nitrate, dilute hydrochloric acid and amino acid; the workpiece is placed in the wet electrochemical joint, the composite coating on the surface of the workpiece generates transfer ion reaction, and a continuous surface joint surface is directly formed on the surface, so that a stable joint surface can generate the joint surface.
The method comprises the following specific steps:
preparing 0.1-0.5M of electrolyte of nickel nitrate/chromium nitrate/dilute hydrochloric acid/amino acid/water;
disposing a conjugate electrode (workpiece A), a conjugate electrode (workpiece B), and a reference electrode;
adjusting the voltage to 1-5V and 1.0-10.0A, referring to the electrochemical workstation, and observing the potential output to a descending trend so as to complete the wet electrochemical bonding process.
The diffusion bonding of the two coatings on the surface of the workpiece to be bonded utilizes the surface microstructure to provide a large range of surface area to increase the space for infiltrating mutual engaging force, voltage and current flow in the joint surface of the two workpieces to provide effective interface bonding, and then the pressure drop is carried out to gradually adjust the joint strength rise of the joint surface so as to achieve the effect of bonding.
Placing the shell-shaped structure with specified joint into two conductive substrates, applying specific voltage and pressure, normally setting voltage at 1-5V, setting current at 1-10A, and vacuum environment.
The process flow is to carry out wet electroforming jointing reaction, maintain effective process by jointing two workpieces in electrolyte, and clamp and contact the joint surfaces of the two workpieces by supplementing a certain amount of metal ion concentration in the electrolyte, so that the joint surfaces of the two workpieces can not only carry out ion exchange in electrochemistry in the conduction process of voltage/current, but also achieve the joint surface jointing and form the effect of a wet electroforming jointing metal coating.
Claims (10)
1. A method of chemical bonding suitable for use with an endoscopic structure, comprising the steps of:
(1) surface treatment
Pretreating the joint surface of the heterogeneous materials to be jointed to expose the materials of the joint surface;
(2) microstructure array preparation
Etching the exposed joint surface to generate a microstructure array pattern in dense arrangement on the surface; then, manufacturing nano-scale micropores on the surface of the pattern;
(3) preparation of composite coating
Respectively carrying out replacement layer growth, seed crystal layer replacement and middle layer plating on the microstructure array pattern of the heterogeneous material to be jointed in sequence to obtain a composite plating layer;
(4) wet electrochemical bonding
The materials to be jointed are respectively connected with the anode and the cathode, ion sources are supplemented through electrolyte under the action of high-voltage current, the composite coating generates transfer ion reaction, and a continuous surface joint surface is directly formed on the joint surface to achieve the joint effect.
2. A chemical bonding method applied to an endoscopic structure as defined in claim 1, wherein said heterogeneous material includes a metallic material, a semiconductor material or a polymer material.
3. A method of chemical bonding adapted for use with an endoscopic structure as defined in claim 1, wherein said surface treatment process of step 1 comprises etching or cleaning or etching plus cleaning.
4. The chemical bonding method for endoscopic structures as defined in claim 1, wherein the micro-structure array preparation in step 2 employs wet etching to imprint the array pattern, and the specific process is as follows:
preparing a mold with a microstructure array, carrying out catalytic corrosion by using an electrolytic reaction suitable for a joint surface material, and reversely etching and copying a microstructure array pattern of the mold on a joint surface.
5. The chemical bonding method for endoscopic structures as defined in claim 1, wherein the microstructure array preparation in step 2 employs dry imprint transfer array pattern, and the specific process is as follows:
preparing a mold with a microstructure array, and forming a microstructure array pattern of the mold on a joint surface by dry electrolytic imprinting suitable for the joint surface material.
6. A method of chemical bonding adapted for endoscopic structures as defined in claim 1, wherein said displacement layer growth of step 3 comprises the steps of:
immersing the joint surface into catalytic electrolytic metal complex solution to enable the metal complex to form a catalytic ion layer on the surface of the microstructure array; the complex liquid is a complex solution of tin dioxide and glycine, cysteine, arginine or serine.
7. The method of claim 1, wherein the step 3 of replacing the seed layer comprises the steps of:
and soaking the joint surface into chloride solution of gold, silver, palladium or platinum, and performing displacement under the catalysis of the catalytic ion layer, so that the catalytic ion layer on the surface of the microstructure array absorbs and displaces to form a metal coating.
8. A method of chemically bonding structures suitable for use in an endoscope according to claim 1 and wherein said intermediate layer plating of step 3 comprises the steps of:
and electroplating nickel, copper, zinc, chromium or titanium on the metal coating on the surface of the microstructure array through three electrodes to obtain an intermediate coating.
9. A method of chemically bonding to an endoscope structure, as described in claim 1, wherein said electrolyte of step 4 is based on a source of nickel ions and comprises nickel sulfate/nickel chloride/hydrochloric acid/additives; wherein the nickel sulfate is 0.5-1M; 0.5-1M of nickel chloride; 0.1-0.2M of hydrochloric acid; the additive is glycine, polyvinyl alcohol or glacial acetic acid.
10. A method of chemically bonding to an endoscopic structure as defined in claim 1, wherein said electrolyte of step 4 is based on a source of chromium ions and comprises chromium sulfate/chromium chloride/hydrochloric acid/sulfuric acid/additives; wherein the chromium sulfate is 0.5-1M; 0.5-1M of chromium chloride; adding 0.1-0.2M of sulfuric acid into hydrochloric acid; the additive is glycine, polyvinyl alcohol or glacial acetic acid.
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