GB1583641A - Process for coating a metal with a porefree film - Google Patents
Process for coating a metal with a porefree film Download PDFInfo
- Publication number
- GB1583641A GB1583641A GB11948/78A GB1194878A GB1583641A GB 1583641 A GB1583641 A GB 1583641A GB 11948/78 A GB11948/78 A GB 11948/78A GB 1194878 A GB1194878 A GB 1194878A GB 1583641 A GB1583641 A GB 1583641A
- Authority
- GB
- United Kingdom
- Prior art keywords
- phenol
- condensation product
- formaldehyde condensation
- process according
- metal surface
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 42
- 229910052751 metal Inorganic materials 0.000 title claims description 32
- 239000002184 metal Substances 0.000 title claims description 32
- 238000000576 coating method Methods 0.000 title claims description 19
- 239000011248 coating agent Substances 0.000 title claims description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 96
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 44
- 239000007859 condensation product Substances 0.000 claims description 32
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 238000001704 evaporation Methods 0.000 claims description 15
- 230000008020 evaporation Effects 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000005260 corrosion Methods 0.000 claims description 5
- 230000007797 corrosion Effects 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011369 resultant mixture Substances 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 2
- 238000004532 chromating Methods 0.000 claims description 2
- 239000000498 cooling water Substances 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000004519 grease Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 238000011282 treatment Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 3
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- VLJSLTNSFSOYQR-UHFFFAOYSA-N 3-propan-2-ylphenol Chemical compound CC(C)C1=CC=CC(O)=C1 VLJSLTNSFSOYQR-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- MQXNNWDXHFBFEB-UHFFFAOYSA-N 2,2-bis(2-hydroxyphenyl)propane Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1O MQXNNWDXHFBFEB-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- WUQYBSRMWWRFQH-UHFFFAOYSA-N 2-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=CC=C1O WUQYBSRMWWRFQH-UHFFFAOYSA-N 0.000 description 1
- HORNXRXVQWOLPJ-UHFFFAOYSA-N 3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-UHFFFAOYSA-N 0.000 description 1
- -1 Awl203 or CaO Chemical class 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- VGIVLIHKENZQHQ-UHFFFAOYSA-N n,n,n',n'-tetramethylmethanediamine Chemical compound CN(C)CN(C)C VGIVLIHKENZQHQ-UHFFFAOYSA-N 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 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
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/60—Deposition of organic layers from vapour phase
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/12—Organic material
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Description
(54) PROCESS FOR COATING A METAL WITH A PORE-FREE FILM
(71) We, BATFELLE-INSTITUT e.V, of of Am Rdmerhof 35, D-6000 Frankfurt
Main 90, Germany, a German Company, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention relates to a process for coating a metal with a pore-free film.
More specifically, the present invention relates to a process which enables thin, adherent, pore-free films to be coated on a metal surface to protect the metal against corrosion. The invention is thus particularly suitable for coating metal components of heat exchangers.
The conventional methods for coating a metal surface with a film include lacquering, dipping, spraying and the application of powder, but all these methods give relá- tively thick films of poor thermal conductivity. It is not possible to employ these conventional methods to give a film which is both thin and porefree.
Very thin and practically pore-free layers can be obtained on any desired surface by the parylene method which comprises pyrolysis of paracyclophanes and subsequent polymerization of the gaseous pyrolysis products. However, the paracyclophanes are very expensive and the method requires a high vacuum and precise temperature regulation during both the pyrolysis and the polymerization. The paralyene method is therefore technically very costly and usually uneconomical.
Coatings may also be obtained from the gas phase by using photolytic polymerization. The disadvantage of this method is that it requires the use of UV radiation, and as such only geometrically simple, easily accessible surfaces can be coated. It is also known to produce thin layers by gas discharge polymerization using for example high frequency generators. Again, this method can only be used to coat geometrically simple, easily accessible surfaces.
It has now been found that pore-free films can be coated on to a metal surface by condensing a phenol vapour on a prepared metal surface, condensing also on the prepared metal surface a vapour of a low molecular weight condensation product of formaldehyde and ammonia or an amine, and then curing the resultant mixture of condensed phenol and formaldehyde condensation product by heating. By this method, thin coatings can be readily produced.
The phenol employed to provide the phenol vapour may be one or more substituted or unsubstituted phenols, for example phenol itself, bisphenol A (4,41 isopropylidenediphenol, m-cresol, 3,5-dimethylphenol, m-chlorophenol, salicylaldehyde, m-isopropylphenol, resorcinol, and 4,41-diphenol. The preferred phenol is bisphenol A and when using this phenol it is particularly preferred that 10 to 30% by weight, referred to the weight of the phenol, of an acid, base or amphoteric metal oxide, e.g. Awl203 or CaO, is added to the bisphenol A before evaporation. The metal oxide performs a complex role but in general it serves to ensure a better surface coating; we believe it acts as a cracking catalyst and that the phenol vapour derived from bisphenol A includes cracked products such as phenol and isopropenylphenol.
Examples of formaldehyde/ ammonia or amine condensation products which can be employed to provide the formaldehyde condensation product vapour include products formed by condensation of formaldehyde with ammonia e.g. hexamethylenetetramine, products formed by condensation of formaldehyde with amines e.g. bis-(dimethylamino)methane, and products formed by condensation of formaldehyde with ammonia or an amine in the presence of phenol e.g. the condensation product of 3 moles formaldehyde, 3 moles dimethylamine and 1 mole phenol, i.e. 2,4,6-tris-(dimethyl- aminomethyl)phenol. More generally, the condensation product will typically hsve a boiling or sublimation point below 300"C.
Mixtures of condensation products may be used, but preferably hexamethylenetetramine is employed.
The mixing ratio of the phenol component to the formaldehyde condensation product may vary within wide limits in the mixture which is condensed on the prepared metal surface; mixtures which consist of 50 to 95% by weight of the phenol and 5 to 50% by weight of the formaldehyde condensation product are preferred.
The phenol component and the formaldehyde condensation product are condensed on a prepared metal surface. The metal surface is prepared by removing grease and other surface soilings which might otherwise prevent a good bond from being obtained between the cured mixture and the metal surface. Conventional treatments such as pickling, phosphating by immersion in a phosphate bath or chromating by immersion in a chromate bath may be employed.
The evaporation of the phenol component and the formaldehyde condensation product is carried out at atmospheric or reduced pressure. They may be evaporated simultaneousely from two different evaporators or in an alternative procedure they are evaporated in succession from the same evaporator. If desired the evaporation of the phenol component and/or the formaldehyde condensation product may be assisted, in which case a flow of inert gas such as nitrogen is typically employed.
Regardless of the technique employed for evaporation, the desired result is to condense a mixture of a phenol and a formaldehyde condensation product on the metal surface. To this end it may be advantageous to cool the surface to speed the physical condensation, for example by employing cooling air or cooling water.
After the evaporation steps the condensed mixture is heated to bring about curing. A suitable temperature is in the range 100 to 250"C, and is preferably in the range 150 to 200"C. The time required for curing can be determined by simple experiment but will usually be one to three hours. The curing then gives a pore-free coating adhering to the metal surface and whose thickness depends on the amount of the mixture condensed on the metal surface. Typically the lawyer will be 1 to 30 s1 thick.
An embodiment of the process provided by the present invention is described in detail in the following example.
Exan1ple A degreased and phosphated iron pipe 2 m long and 3 cm in diameter was clamped in a glass laboratory coating apparatus and cooled by passing water therethrough. 0.3 mg/cm2 of hexamethylenetetramine was firstly evaporated from an evaporator at 210 C onto the cooled iron pipe, followed by 2.0 mg/cm2 of bisphenol A at 250"C, nitrogen being passed over the pipe during the procedure. The nitrogen flow also served to assist the evaporation. The bisphenol A to be evaporated contained 20% aluminium oxide and as such the phenol condensed on the pipe comprised bisphenol A and phenolic products derived therefrom. After the evaporation, cooling of the iron pipe was discontinued and instead the latter was heated for 30 minutes at llO"C and then for 30 minutes at 1800C by passing hot air therethrough, the evaporated components thereby being cured.
A golden coating 8 jt thick having the following properties was obtained: porosity (DIN 53 161): P1 to P2 porosity (DIN 54 161): pore-free grid section test (DIN 51 151): GtO to Gtl pencil hardness test: 1 to 2.
When employed as part of a heat exchanger exposed to boiling seat water the coated iron pipe did not show any signs of corrosion after six months operation.
It will thus be seen that the process provided by the invention enables one to prepare corrosion resistant coatings using relatively inexpensive starting materials. The steps involved of condensation and curing can be carried out using technically simple apparatus and the expensive equipment such as UV radiators or high frequency generators which are required by the prior art methods are no longer needed. In addition, large objects having complicated surface configurations may be satisfactorily coated.
WHAT WE CLAIM IS:- 1. A process for coating a metal with a pore-free film which comprises condensing a phenol vapour on a prepared metal surface, condensing also on the prepared metal surface a vapour of a low molecular weight condensation product of formaldehyde and ammonia or an amine, and then curing the resultant mixture of condensed phenol and formaldehyde condensation product by heating.
2. A process according to claim 1, wherein the resultant condensed mixture consists of 50 to 95% by weight of a phenol and 5 to 50% by weight of a formaldehyde condensation product.
3. A process according to claim 1 or claim 2, wherein a phenol and a formaldehyde condensation product are simultaneously evaporated from two different evaporators.
4. A process according to claim 1 or claim 2, wherein a phenol and a formaldehyde condensation product are evaporated in succession from the same evaporator.
5. A process according to any one of claims 1 to 4, wherein the phenol employed to provide the phenol vapour is bisphenol A.
6. A process according to claim 5,
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (11)
1. A process for coating a metal with a pore-free film which comprises condensing a phenol vapour on a prepared metal surface, condensing also on the prepared metal surface a vapour of a low molecular weight condensation product of formaldehyde and ammonia or an amine, and then curing the resultant mixture of condensed phenol and formaldehyde condensation product by heating.
2. A process according to claim 1, wherein the resultant condensed mixture consists of 50 to 95% by weight of a phenol and 5 to 50% by weight of a formaldehyde condensation product.
3. A process according to claim 1 or claim 2, wherein a phenol and a formaldehyde condensation product are simultaneously evaporated from two different evaporators.
4. A process according to claim 1 or claim 2, wherein a phenol and a formaldehyde condensation product are evaporated in succession from the same evaporator.
5. A process according to any one of claims 1 to 4, wherein the phenol employed to provide the phenol vapour is bisphenol A.
6. A process according to claim 5,
wherein 10 to 30% by weight, referred to the weight of the phenol, of an acid, base or amphoteric metal oxide is added to the bisphenol A before evaporation.
7. A process according to claim 6, wherein the metal oxide is aluminium oxide.
8. A process according to any one of the preceding claims, wherein the formaldehyde condensation product is hexamethylenetetramine.
9. A process according to any preceding claim wherein the phenol vapour and/or formaldehyde condensation product vapour are produced by assisted evaporation of a phenol and/or formaldehyde condensation product, as the case may be.
10. A process for coating a metal with a pore-free film, the process being substantially as described in the Example hereinbefore.
11. A metal object with a pore-free film on its surface when produced by a process according to any one preceding claim.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2712903A DE2712903C3 (en) | 1977-03-24 | 1977-03-24 | Process for the production of thin, firmly adhering, pore-free coatings on metal surfaces |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1583641A true GB1583641A (en) | 1981-01-28 |
Family
ID=6004508
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB11948/78A Expired GB1583641A (en) | 1977-03-24 | 1978-03-28 | Process for coating a metal with a porefree film |
Country Status (8)
| Country | Link |
|---|---|
| BE (1) | BE865143A (en) |
| DD (1) | DD135090A5 (en) |
| DE (1) | DE2712903C3 (en) |
| ES (1) | ES468106A1 (en) |
| FR (1) | FR2384554A1 (en) |
| GB (1) | GB1583641A (en) |
| IT (1) | IT1102831B (en) |
| NL (1) | NL7802293A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3125113C1 (en) * | 1981-06-26 | 1982-11-11 | Battelle-Institut E.V., 6000 Frankfurt | "Process for the production of anti-corrosion layers on metallic surfaces" |
| DE3915080A1 (en) * | 1989-05-09 | 1990-11-15 | Basf Lacke & Farben | METHOD FOR COATING ELECTRICALLY CONDUCTIVE SUBSTRATES |
-
1977
- 1977-03-24 DE DE2712903A patent/DE2712903C3/en not_active Expired
-
1978
- 1978-03-02 NL NL7802293A patent/NL7802293A/en not_active Application Discontinuation
- 1978-03-09 IT IT48367/78A patent/IT1102831B/en active
- 1978-03-21 ES ES468106A patent/ES468106A1/en not_active Expired
- 1978-03-21 BE BE186140A patent/BE865143A/en not_active IP Right Cessation
- 1978-03-22 FR FR7808356A patent/FR2384554A1/en active Granted
- 1978-03-22 DD DD78204353A patent/DD135090A5/en unknown
- 1978-03-28 GB GB11948/78A patent/GB1583641A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DD135090A5 (en) | 1979-04-11 |
| IT1102831B (en) | 1985-10-07 |
| FR2384554B3 (en) | 1980-11-14 |
| ES468106A1 (en) | 1979-01-01 |
| DE2712903A1 (en) | 1978-09-28 |
| FR2384554A1 (en) | 1978-10-20 |
| NL7802293A (en) | 1978-09-26 |
| DE2712903C3 (en) | 1981-10-15 |
| DE2712903B2 (en) | 1980-10-23 |
| IT7848367A0 (en) | 1978-03-09 |
| BE865143A (en) | 1978-07-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed [section 19, patents act 1949] | ||
| PCNP | Patent ceased through non-payment of renewal fee |