EP3820629A1 - Procédé de formation d'un film organique polymerique a la surface d'un substrat metallique mettant en ?uvre un gel - Google Patents
Procédé de formation d'un film organique polymerique a la surface d'un substrat metallique mettant en ?uvre un gelInfo
- Publication number
- EP3820629A1 EP3820629A1 EP19791310.6A EP19791310A EP3820629A1 EP 3820629 A1 EP3820629 A1 EP 3820629A1 EP 19791310 A EP19791310 A EP 19791310A EP 3820629 A1 EP3820629 A1 EP 3820629A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- tetrafluoroborate
- gel
- substrate
- film
- chosen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 29
- 239000002184 metal Substances 0.000 title claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 36
- 239000003349 gelling agent Substances 0.000 claims abstract description 25
- 229920000412 polyarylene Polymers 0.000 claims abstract description 12
- -1 aryl diazonium salt Chemical class 0.000 claims description 42
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 239000012954 diazonium Substances 0.000 claims description 9
- 229920000159 gelatin Polymers 0.000 claims description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 108010010803 Gelatin Proteins 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 235000019322 gelatine Nutrition 0.000 claims description 7
- 235000011852 gelatine desserts Nutrition 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229920001282 polysaccharide Polymers 0.000 claims description 4
- 239000005017 polysaccharide Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 244000007835 Cyamopsis tetragonoloba Species 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000004965 chloroalkyl group Chemical group 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 3
- 150000004676 glycans Chemical class 0.000 claims description 3
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- JLLBHFPMIDLVRO-UHFFFAOYSA-M 4-aminobenzenediazonium;chloride Chemical compound [Cl-].NC1=CC=C([N+]#N)C=C1 JLLBHFPMIDLVRO-UHFFFAOYSA-M 0.000 claims description 2
- ICMFHHGKLRTCBM-UHFFFAOYSA-N 4-nitrobenzenediazonium Chemical compound [O-][N+](=O)C1=CC=C([N+]#N)C=C1 ICMFHHGKLRTCBM-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229920000936 Agarose Polymers 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001449 anionic compounds Chemical class 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 210000000988 bone and bone Anatomy 0.000 claims description 2
- 229920001525 carrageenan Polymers 0.000 claims description 2
- 235000010418 carrageenan Nutrition 0.000 claims description 2
- 210000000845 cartilage Anatomy 0.000 claims description 2
- 229940005989 chlorate ion Drugs 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 229910001412 inorganic anion Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 150000002891 organic anions Chemical class 0.000 claims description 2
- 235000014594 pastries Nutrition 0.000 claims description 2
- 108090000623 proteins and genes Proteins 0.000 claims description 2
- 102000004169 proteins and genes Human genes 0.000 claims description 2
- 229920001285 xanthan gum Polymers 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- BAJJCUMRSLDNPB-UHFFFAOYSA-O 4-acetamidobenzenediazonium Chemical compound CC(=O)NC1=CC=C([N+]#N)C=C1 BAJJCUMRSLDNPB-UHFFFAOYSA-O 0.000 claims 1
- KXBKHYBYIHGSIE-UHFFFAOYSA-M 4-cyanobenzenediazonium;chloride Chemical compound [Cl-].N#CC1=CC=C([N+]#N)C=C1 KXBKHYBYIHGSIE-UHFFFAOYSA-M 0.000 claims 1
- 239000000499 gel Substances 0.000 description 37
- 230000015572 biosynthetic process Effects 0.000 description 19
- 239000010410 layer Substances 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 8
- 229910000838 Al alloy Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229920002907 Guar gum Polymers 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 235000010417 guar gum Nutrition 0.000 description 5
- 239000000665 guar gum Substances 0.000 description 5
- 229960002154 guar gum Drugs 0.000 description 5
- 230000002269 spontaneous effect Effects 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 230000000873 masking effect Effects 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000004566 IR spectroscopy Methods 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003636 chemical group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MUPGQOVOZGOKRU-UHFFFAOYSA-M 4-(aminomethyl)benzenediazonium;chloride Chemical compound [Cl-].NCC1=CC=C([N+]#N)C=C1 MUPGQOVOZGOKRU-UHFFFAOYSA-M 0.000 description 1
- RGCITEKHKXPDDH-UHFFFAOYSA-N 4-(diethylamino)benzenediazonium Chemical compound CCN(CC)C1=CC=C([N+]#N)C=C1 RGCITEKHKXPDDH-UHFFFAOYSA-N 0.000 description 1
- NDBJTKNWAOXLHS-UHFFFAOYSA-N 4-methoxybenzenediazonium Chemical compound COC1=CC=C([N+]#N)C=C1 NDBJTKNWAOXLHS-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- FZNPEFOJLMGAHE-UHFFFAOYSA-N N#[N+]C1=CC=CC=C1CC([O-])=O Chemical compound N#[N+]C1=CC=CC=C1CC([O-])=O FZNPEFOJLMGAHE-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
- B05D7/142—Auto-deposited coatings, i.e. autophoretic coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
Definitions
- the invention relates to a process for forming a polymeric organic film of the polyarylene type on the surface of a specific metallic substrate which does not require the intervention of an electrochemical cell and / or of an external electrical initiation, for example, by application of a potential, the formation of the organic film occurring spontaneously by simple contacting between the film precursors and the metal substrate to be coated.
- the process according to the invention which makes it possible to graft a large variety of polymer films onto very diverse surfaces, both in terms of their dimensions and their configuration, is likely to find applications in all fields where the one may wish to endow such surfaces with particular properties such as, for example, corrosion resistance properties, tribological properties, hydrophilic properties or, on the contrary, hydrophobic properties and electrical insulation properties .
- the method according to the invention can also be used to cover the surface of a metal substrate with a polymer film suitable for serving as an adhesion primer for the subsequent fixing, on this same surface, of molecules of interest such as, for example , biologically active substances, for fixing paints in particular in the aeronautical, railway or automobile fields or even for the complexing of metallic element (s) capable of being reduced later to form a layer of metallization.
- molecules of interest such as, for example , biologically active substances
- this process consists in reducing, by application of a cathodic current, the diazonium cations of the aryldiazonium salt, in solution in a solvent, into aryl radicals.
- the aryl radicals thus formed can then react, covalently, with the surface on which the grafting is to be carried out and form an organic layer of aryl groups on this surface.
- These aryl groups can be substituted by one or more functional groups, for example of the nitro type, if the aryl group of the aryl diazonium salt which is used is itself substituted by this or these functional groups.
- a chemical reducing agent of the hypophosphorous acid (H 3 PO 2 ), ascorbic acid, iron powder or hydroquinone type is added to the solution of aryldiazonium salt.
- aryldiazonium salt has proven to be an interesting way to functionalize a wide range of carbon materials including, in particular, carbon nanotubes (CNT) as well as metals such as gold, platinum and nickel, however, it leads to the formation of organic films whose thickness is generally less than a few tens of nanometers and sometimes only corresponds to a bilayer of aryl groups.
- CNT carbon nanotubes
- metals such as gold, platinum and nickel
- the inventors therefore set themselves the goal of providing a process which makes it possible to form a polymeric film, and more specifically, a polyarylene type polymeric film on a specific metal substrate, which does not require the assistance of '' an electrochemical cell for the application of a current and which allows, moreover, the obtaining of a localized polymeric film without requiring a stage of saving or masking of the parts of substrate which must not be coated of the film.
- the invention relates to a process for forming a polymeric film of the polyarylene type on all or part of a metal substrate, characterized in that the film is formed spontaneously by the simple fact of bringing the or the parts of the substrate to be coated with the film with a gel comprising at least one aryl diazonium salt and at least one gelling agent and characterized in that the metallic substrate is a reducing metallic substrate.
- the formation of a polymeric film of the polyarylene type is carried out by simple contacting of the part or parts of a reducing metallic substrate which it is desired to coat with a gel comprising at least at least one aryl diazonium salt and at least one gelling agent.
- a gel comprising at least at least one aryl diazonium salt and at least one gelling agent.
- simple brought into contact it is understood that the film is formed by the simple fact of this contacting, that is to say without reduction treatment other than bringing the gel into contact with the reducing metallic substrate , for example, without the need for the application of an external reduction potential (i.e., for example, by means of an electrochemical cell connected to the substrate to be coated) or of another reduction treatment, such as '' UV or visible irradiation treatment.
- the gel can be integrated into different application devices (for example, an application pen, a tube or a device of the "roll-on” type) and can have its composition adapted depending on the needs and the desired result (for example, by the choice of the gelling agent (s), the aryl diazonium salt (s), the aryl diazonium salt concentration (s), the duration of contacting);
- the gel brought into contact a first time can be removed after having acted and repositioned on another part or on another place of the same part , this withdrawal and repositioning can be reiterated, as soon as the initial concentration of the gel in active species (in this case, here, the aryldiazonium salt or salts) is sufficient.
- active species in this case, here, the aryldiazonium salt or salts
- the invention uses a gel comprising at least one aryl diazonium salt and at least one gelling agent for the spontaneous formation of a film on the surface of a reducing metallic substrate.
- a chemical system consisting of a three-dimensional network consisting of gelling agent (s) (which can also be qualified as compound (s) with property (colloidal) forming a matrix (which constitutes a solid continuous phase), within which a liquid phase is trapped (in this case, the liquid phase trapped within the matrix comprises, conventionally, according to the invention, the aryldiazonium salt).
- the gels used in the process of the invention can comprise, as gelling agent (s) (or compound (s) with colloidal property (s)):
- polysaccharides for example, chosen from agaroses, chitosans, xanthans, carrageenans, guar gums and mixtures thereof;
- the gelling agent or agents used for implementing the method of the invention are polysaccharides of the guar gum family or are gelatins.
- the amount of gelling agents will be chosen as a function of the viscosity desired for the gel, which may in particular be dependent on the deposition technique adopted for bringing the gel into contact with the metal substrate, at the surface of which one wishes to form a film.
- the liquid phase included in the gel conventionally comprises one or more solvents, in which the aryliazonium salt or salts are conventionally dissolved.
- the solvent (s) can be organic solvents, water and mixtures thereof.
- the liquid phase included in the gel can consist of an acidic aqueous solution comprising the aryliazonium salt (s), advantageously, in a dissolved form.
- an acidic aqueous solution mention may be made of an aqueous solution comprising at least one strong acid and, more particularly, a mineral acid, such as:
- the sulfuric acid H 2 S0 4 in particular when the reducing metal substrate is made of aluminum or aluminum alloy;
- hydrochloric acid mixed with sulfuric acid especially when the reducing metal substrate is made of iron or an iron alloy;
- reducing metallic substrate is made of titanium or titanium alloy
- -nitric acid sulfuric acid, mixtures of nitric acid and sulfuric acid, chromic acid, phosphoric acid, especially when the metal substrate is made of magnesium or magnesium alloy.
- an acidic aqueous solution in addition to facilitating the solubilization of the aryldiazonium salt (s), may help to remove, if where appropriate, the passivation layer existing on the surface of the reducing metal substrate, which passivation layer is conventionally an oxide layer formed spontaneously when the reducing metal substrate is exposed to air and can thus hinder the formation of the film.
- the aryldiazonium salt which is chosen in particular as a function of the end use of the metal substrate and of the possible functionalities which it is desired to bring to this substrate by the polyarylene film, can be any salt of formula + N 2 -Ar, X in which:
- Ar represents an aryl group, this aryl group possibly comprising one or more aromatic or heteroaromatic rings condensed or not, this cycle or at least one of these cycles possibly being mono- or polysubstituted;
- X represents a monovalent anion
- the substituent or substituents carried by the aromatic ring or at least one of the aromatic rings of the aryl group can be chosen from very numerous chemical groups among which mention may, for example, be made of alkyl or haloalkyl groups of the type chloro- or fluoroalkyls, alkoxy, haloalkoxy, nitro, cyano, aldehyde, hydroxyl, ketone, carbonyl, carboxyl, ester, ether, amine, amide, nitrile, sulfonic, halogen atoms.
- the group Ar represents a phenyl group optionally substituted by at least one substituent chosen from alkyl, haloalkyl groups of the chloro- or fluoroalkyl, alkoxy, haloalkoxy, nitro, cyano, aldehyde, hydroxyl, ketone, carbonyl, carboxyl or ester type, ether, amine, amide, nitrile, sulfonic, halogen atoms, the substituent being, for example, a nitro group.
- the group Ar can represent a phenyl group substituted by at least one nitro group.
- X is an inorganic anion such as a halide ion such as a bromide ion (Br), iodide (I) or chloride (CI), a tetrahalogenoborate ion such as a tetrafluoroborate ion (BF 4 ), a hydrogen sulfate ion (HS0 4 ), a dihydrogen phosphate ion (FhPCV), a nitrate ion (NO 3 ) or a chlorate ion (CIO3-).
- a halide ion such as a bromide ion (Br), iodide (I) or chloride (CI)
- a tetrahalogenoborate ion such as a tetrafluoroborate ion (BF 4 ), a hydrogen sulfate ion (HS0 4 ), a dihydrogen phosphate ion (FhPCV), a
- aryldiazonium salts which may be used, mention may be made of phenyldiazonium tetrafluoroborate, 4-methylphenyldiazonium tetrafluoroborate, 4-nitrophenyldiazonium tetrafluorobrate, 4-carboxyphenyldiazor tetrafluoroborate, tetrafluoretrafluoride carboxymethylphenyldiazonium, 4-chloromethylphenyldiazonium tetrafluoroborate, 4-bromophenyldiazonium tetrafluoroborate, tetrafluoroborate
- the aryl group of the aryldiazonium salt is a phenyl group, optionally carrying one or more substituents, whereby the polyarylene film which is grafted is a film of a polyphenylene.
- the aryl group of the aryldiazonium salt is a phenyl group substituted by a nitro group, in which case the film formed is a film of a poly (nitrophenylene).
- the substrate on the surface of which a polymeric film of the polyarylene type is formed, is a reducing metallic substrate, that is to say a substrate comprising one or more metallic elements, at least one of which of these metallic elements is capable of reducing the aryliazonium salt or salts.
- a reducing metal substrate suitable for implementing the invention can be a substrate comprising (or consisting of) aluminum, titanium, magnesium, zinc, copper, iron, manganese, cobalt, nickel and alloys thereof.
- it may specifically be aluminum alloys, copper and zinc alloys (such as brass) or iron alloys (such as stainless steels ).
- the duration of contacting can be chosen by a person skilled in the art so as to obtain the desired film, the obtaining of the film being able to be verified by analysis techniques such as infrared spectroscopy.
- the gel is brought into contact with the reducing metallic substrate by any deposition techniques compatible with a gel and, in particular, by one of the following techniques:
- doctor blade coating also known by the English name “doctor blade coating”
- an application system of the “roll-on” type (which can also be called a ball applicator, it being understood that the ball is the gel dispensing element);
- the contacting can be carried out by prior cutting of a part formed from said gel and the deposition of said part on the surface of the substrate, on which it is desired to obtain the formation of a film.
- the method of the invention may also comprise a prior step of preparation of the gel comprising a step of bringing the different constituent ingredients of the gel into contact, the methods of this contact being dependent on the ingredients used (in particular, the nature of the 'gelling agent used).
- the preparation can comprise, for example, the following operations:
- an operation for preparing an acidic aqueous solution comprising the aryliazonium salt (s);
- the preparation of the gel can comprise, for example, the following operations:
- an operation for preparing an acidic aqueous solution comprising the aryliazonium salt (s);
- the prepared gels can advantageously be stored in a cold enclosure, for example, a refrigerator.
- the formation of the film (s) on the surface of the reducing metal substrate according to the method of the invention results in a grafting covalent, that is to say a grafting which involves the formation of covalent bonds between the polyarylene film and the reducing metallic substrate.
- the film or films coating, in whole or in part, the substrate can serve as a primary adhesion layer, that is to say a layer which will allow, thanks to the chemical groups which they carry the adhesion of another layer. More specifically, the film or films can serve as a primary adhesion layer for the application of a paint.
- the film or films coating, in whole or in part, the substrate can also perform the function of complexing layer of metallic element (s), since this or these films comprise at least one organic group capable of complexing (for example, a carboxyl or carboxylate group) the desired metallic element or elements.
- the metal element (s) thus complexed can then be reduced to form a metallization layer on the surface of the film (s).
- FIGS. 1 to 3 represent IR spectra illustrating the evolution of the transmittance T (in%) as a function of the number of N waves (in cm 4 ), these spectra being obtained in the context of the implementation of examples 1 and 2 presentations below.
- This example illustrates the formation of a poly (4-nitrophenylene) film on the surface of an aluminum alloy substrate in accordance with the process of the invention, the reagents and objects used being the following: -4-nitrophenyldiazonium tetrafluoroborate;
- a substrate made of an aluminum alloy known as an AI2024 alloy.
- the AI2024 alloy is a high tensile strength alloy, generally used in the aeronautical field and considered as ideal for shaping and machining.
- composition of this alloy is as follows:
- 4-nitrophenyldiazonium tetrafluoroborate in powder form (876.6 mg for IL) is added to a 1 M aqueous sulfuric acid solution (1 L), the concentration of 4-nitrophenyldiazonium tetrafluoroborate being thus 3.7 * 10 3 M.
- the resulting mixture is passed through ultrasound for 10 minutes.
- the gelling agent of the guar gum type (16 g for IL) is added gradually, at room temperature and manually using a spatula.
- the gel obtained is then applied with a spatula at the rate of approximately 0.2 ml / cm 2 to the substrate made of AI2024 alloy and left to stand for 5 minutes.
- the substrate thus coated is then thoroughly rinsed with water and then dried under compressed air.
- the substrate thus treated is characterized by infrared spectroscopy, the spectrum obtained being illustrated by Figure 1 attached. It emerges from this spectrum, two intense bands at 1350 and 1520 cm 1 characteristic of the presence of nitro-NO 2 groups and another band at 1600 cm 1 characteristic of the presence of phenyl groups. This spectrum confirms the presence of a poly (4-nitrophenyl) film on the surface of the substrate.
- the substrate is then passed through ultrasound for 5 minutes in ethanol.
- an IR spectrum is again recorded as illustrated by FIG. 2 attached in the appendix. It remains unchanged compared to the previous spectrum, which attests to the fact that the film is not physisorbed but is grafted covalently to the substrate.
- This example illustrates the formation of a poly (4-nitrophenylene) film on the surface of an aluminum alloy substrate in accordance with the process of the invention, the reagents and objects used being the following:
- gelatin as a gelling agent, gelatin
- 4-nitrophenyldiazonium tetrafluoroborate in powder form (876.6 mg for IL) is added to a 1 M aqueous sulfuric acid solution (1 L), the concentration of 4-nitrophenyldiazonium tetrafluoroborate being thus 3.7 * 10 3 M.
- the resulting mixture is passed through ultrasound for 10 minutes.
- the gelling agent of the gelatin type (18.9 g for IL) is immersed in cold water for 5 minutes to hydrate it. It is then drained and added to the previous mixture at 40 ° C. Manual mixing is carried out with a spatula and the whole is placed in the refrigerator for 3 hours.
- the gel obtained is then applied with a spatula at the rate of approximately 0.2 ml / cm 2 to an AI2024 alloy substrate and left to stand for 5 minutes.
- the substrate thus coated is then thoroughly rinsed with water and then dried under compressed air.
- the substrate thus treated is characterized by infrared spectroscopy, the spectrum obtained being illustrated by Figure 3 attached. It emerges from this spectrum, two intense bands at 1350 and 1520 cm 1 characteristic of the presence of nitro-NO 2 groups and another band at 1600 cm 1 characteristic of the presence of phenyl groups. This spectrum confirms the presence of a poly (4-nitrophenyl) film on the surface of the substrate.
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Abstract
Description
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1856296A FR3083546B1 (fr) | 2018-07-09 | 2018-07-09 | Procede de formation d'un film organique polymerique a la surface d'un substrat metallique mettant en œuvre un gel |
PCT/FR2019/051692 WO2020012102A1 (fr) | 2018-07-09 | 2019-07-08 | Procédé de formation d'un film organique polymerique a la surface d'un substrat metallique mettant en œuvre un gel |
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EP3820629A1 true EP3820629A1 (fr) | 2021-05-19 |
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ID=65031393
Family Applications (1)
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EP19791310.6A Pending EP3820629A1 (fr) | 2018-07-09 | 2019-07-08 | Procédé de formation d'un film organique polymerique a la surface d'un substrat metallique mettant en ?uvre un gel |
Country Status (3)
Country | Link |
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EP (1) | EP3820629A1 (fr) |
FR (1) | FR3083546B1 (fr) |
WO (1) | WO2020012102A1 (fr) |
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Publication number | Priority date | Publication date | Assignee | Title |
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FR2916766B1 (fr) * | 2007-06-01 | 2009-09-11 | Commissariat Energie Atomique | Procede de formation d'un film organique mettant en oeuvre un gel, ledit gel et son utilisation. |
FR2973036B1 (fr) * | 2011-03-22 | 2013-04-26 | Commissariat Energie Atomique | Procede de preparation d'un film organique a la surface d'un support solide par transfert ou par projection |
FR2991887B1 (fr) * | 2012-06-19 | 2014-07-18 | Commissariat Energie Atomique | Procede de greffage covalent d'un film d'un polyarylene sur une surface conductrice ou semi-conductrice de l'electricite |
FR3014116A1 (fr) * | 2013-12-04 | 2015-06-05 | Commissariat Energie Atomique | Primaire d'adherence pour peinture |
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2018
- 2018-07-09 FR FR1856296A patent/FR3083546B1/fr active Active
-
2019
- 2019-07-08 WO PCT/FR2019/051692 patent/WO2020012102A1/fr unknown
- 2019-07-08 EP EP19791310.6A patent/EP3820629A1/fr active Pending
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Publication number | Publication date |
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WO2020012102A1 (fr) | 2020-01-16 |
FR3083546B1 (fr) | 2022-04-01 |
FR3083546A1 (fr) | 2020-01-10 |
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