CN106167897A - A kind of metal surface film build method of hydrolyzable polymer - Google Patents
A kind of metal surface film build method of hydrolyzable polymer Download PDFInfo
- Publication number
- CN106167897A CN106167897A CN201610553970.3A CN201610553970A CN106167897A CN 106167897 A CN106167897 A CN 106167897A CN 201610553970 A CN201610553970 A CN 201610553970A CN 106167897 A CN106167897 A CN 106167897A
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- Prior art keywords
- sample
- deionized water
- gained
- film
- metal
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- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
-
- 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
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Abstract
The invention belongs to chemical membrane field, be specifically related to the metal surface film build method of a kind of hydrolyzable polymer.The polymer that the present invention the provides film build method in metal surface mainly comprises the steps that after pending for metal sample deionized water supersound washing, removes greasy dirt or the corrosion on surface；By gained metal sample in being positioned in this poly-vinyl alcohol solution；Gained metal sample is positioned in drying baker and is dried；Gained sample is positioned in deionized water flushing, is positioned in drying baker and is dried；Gained sample is positioned in photoelectron spectrograph and detects.It is that the coating process mainly in combination with mode can realize the most firm application with chemical bonds, is to use novel environment-friendly water-based paint as coating.
Description
Technical field
The invention belongs to chemical membrane field, be specifically related to the metal surface film build method of a kind of hydrolyzable polymer.
Background technology
Polyvinyl alcohol (PVA), organic compound, it is dissolved in water, is important industrial chemicals.Water-solubility PVA film is in state
A kind of novel plastic product shown up prominently on border, it make use of the film property of PVA, water and biological two kinds of degradation characteristics, can be complete
Degradable is CO2 and H2O, the high-new environment-friendly materials of green being worthy of the name.China's water-solubility PVA film development also in
Starting stage, industrialness research and development just really launched between nearly 5 years, be mainly used in embroider and water transfer (glass, pottery,
The colored printing of electric appliance casing etc.) two fields, PVA year usage amount about 10000t in this respect.There is no in metal surface
The PVA film build method of effect.
Additionally, adopt the polymer coating of application at present and metallic substrates, especially high grade alloy (such as 316L rustless steel)
Use physical connection method.Generally use throw shot-blast process to metal surface polishing coarse after carry out application.There is certain in this method
A little shortcoming and defect, mainly show as painting adhesion difference and intensity are unstable, cannot use environment-friendly water-based paint, rough surface
Cause paint waste, surface undulation to cause easily and form spot corrosion etc., significantly reduce service life and the use of paint
Effect.As the film forming of water-solubility PVA, there is no related invention at present and occur.
At present, the coating such as paint and metallic substrates especially high grade alloy (such as 316L rustless steel) typically use physics company
Connect method.Generally use throw shot-blast process to metal surface polishing coarse after carry out application.This method exist some shortcoming and
Deficiency, mainly shows as painting adhesion difference and intensity is unstable, environment-friendly water-based paint, rough surface cannot be used to cause paint
Paint waste, surface undulation cause and easily form spot corrosion etc..
Summary of the invention
It is an object of the invention to provide the metal surface film build method of a kind of hydrolyzable polymer, it is achieved coating and gold
Belong to the chemical bonds of substrate, improve service life and the performance of polymer coating, the chemical chain of coating and metallic substrates can be realized
Connect, make the polymer coating can be with direct formation of film at surface at smooth metal surface.This film layer can be hydrolyzed within a certain period of time, with
Reach environmental protection release and other effect.
The polymer that the present invention the provides film build method in metal surface mainly comprises the steps that
(1) by after pending for metal sample deionized water supersound washing, greasy dirt or the corrosion on surface is removed.Treat that surface is clean
After, it is positioned over 70 DEG C of dry 5 min in drying baker, or at 20-30 DEG C of air drying 1-2h, with surface noresidue water droplet for closing
Lattice.
Sample is soaked in 20-30 DEG C, the 2-3mol/L diphosphonic acid (such as 1-hydroxy ethylidene-1,1-diphosphonic acid, HEDP) configured with deionized water
In solution 2-5 minute, carry out 1-hydroxy ethylidene-1,1-diphosphonic acid surface chemistry dress and change the preparation of thin film.It is positioned in drying baker after taking-up
50-70 DEG C of dry 5-10 min, or at 20-30 DEG C of air drying 2-4h, allows the film drying molding of preparation.Treat sample surfaces
Without obvious liquid or colloid, with deionized water lavage specimens product surface 1-3 min, rinse out unnecessary 1-hydroxy ethylidene-1,1-diphosphonic acid crystallization
Residual, the remaining 1-hydroxy ethylidene-1,1-diphosphonic acid metal surface chemical conversion film being difficult to be rinsed.
(2) prepare 0.25-1%'s with the water-soluble poval (PVA) of average molar mass 30000-70000 and deionized water
PVA solution, is positioned over gained metal sample in step (1) in this polyvinyl alcohol (PVA) solution in 20-30 DEG C, 20-30 DEG C of leaching
Bubble 1-2h, makes polyvinyl alcohol homogeneous film formation on the chemical conversion film of 1-hydroxy ethylidene-1,1-diphosphonic acid metal surface；
(3) step (2) gained metal sample is positioned over 60 DEG C dry 1 hour in drying baker；
(4) step (3) gained sample is positioned in deionized water flushing 30 seconds, is positioned over 50-70 DEG C of dry 5-in drying baker
10 min, or at 20-30 DEG C of air drying 2-4h, allow the film drying molding of preparation；
(5) step (4) gained sample is positioned in photoelectron spectrograph detects.
The main innovation point of patent is in the formation of the conversion chemosphere based on diphosphonic acid phosphating coat.Utilize x-ray photoelectron energy
Spectrometer (XPS) is characterized: without this layer change film, the water-soluble poval of 1% cannot in metal surface film forming,
See Fig. 1 upper left, but after forming this layer conversion film, the water-soluble poval of 1% can be shown in effectively in metal surface film forming
Fig. 1 upper right portion.This tunic has preferable stability in atmosphere, sees Fig. 1 lower right-most portion；Soak in aqueous and have portion in 2 days
Component polyethylene alcohol film starts hydrolysis, Fig. 1 bottom left section.These results suggest that polyvinyl alcohol film can be effectively formed, and at sky
Gas has certain stability, can slowly hydrolyze in water.
This is that the coating process mainly in combination with mode can realize the most firm application with chemical bonds, is to use novel environment friendly
Aqueous paint is as coating.In addition it is required for throwing shot-peening or the method on other polishing surface, smooth painting attractive in appearance can be realized
Dress, saves paint, it is not easy to form the corrosion harmfulnesses such as spot corrosion.
Accompanying drawing 1 is the experimental procedure schematic diagram of the present invention；
Accompanying drawing 2 is the effect display schematic diagram of the present invention.
Fig. 1 100 is the pending sample of metal shown in step A,
In figure: foreign material or the pollutant 11 such as metallic substrates 12 and oxide on surface (such as rust), in the middle of it, it is demarcated as fresh metal
Surface 13.
In Fig. 1 shown in step B, in a step 101, by pending for metal sample 100 with after deionized water supersound washing, put into
In room temperature 3mol/L binary organic phosphoric acid (such as 1-hydroxy ethylidene-1,1-diphosphonic acid) solution, soak 2 minutes, remove oxide on surface (ferrum
Rust) etc. foreign material 10, and in fresh metal surface 13 formed one layer of chemically reactive layer 14 based on diphosphate.This layer of salt
Formation refers to quote document.
In Fig. 1 shown in step C, in a step 102, metal sample is taken out in the sample and is dried in atmosphere, chemically reactive layer
Can form one layer of diphosphonic acid phosphating coat 15 on 14, thickness can be controlled in 0.6-100 nanometer, and unnecessary phosphating coat can be rushed by current
Wash off.
In Fig. 1 shown in step D, in step 103, after phosphating coat 15 is formed, water-soluble poval will be at surface filming 16.
In Fig. 2, M-metal；O-oxide and hydroxide；P-oxide-free nanometer layer；HA-hydroxyapatite；G-medical science function
Material (heparin)；I-metal；Ii-oxide-free artistic face is modified；Iii-hydroxyapatite is in the self assembly on surface；Iv-merit
Two kinds of possible absorption shapes of energy coating-to be characterized；The possible absorption shape of two kinds of v-functional coating-to be characterized.
Embodiment:
Embodiment 1:
(1) it is dried being positioned in drying baker after 316L stainless steel carrier deionized water supersound washing 1 hour；
(2) being positioned in 1% polyvinyl alcohol (PVA) solution by (1) step gained stainless steel carrier, 20 DEG C are soaked 1 hour；(3) will
(2) step gained stainless steel carrier is positioned over 60 DEG C dry 1 hour in drying baker；
(4) (3) step gained sample is positioned in deionized water flushing 30 seconds；
(5) (4) step gained sample is positioned over 60 DEG C dry 1 hour in drying baker；
(6) (5) step gained sample is positioned in photoelectron spectrograph detects.
Embodiment 2:
(1) by 316L stainless steel carrier with after deionized water supersound washing, 20 DEG C are soaked in 5MOL/L 1-hydroxy ethylidene-1,1-diphosphonic acid and (depend on
For phosphonic acids, HEDP) in 2 minutes, be positioned in drying baker be dried 1 hour；
(2), after (1) step gained stainless steel carrier being washed with deionized, it is positioned in 1% polyvinyl alcohol (PVA) solution, 20
DEG C soak 1 hour；
(3) (2) step gained stainless steel carrier is positioned over 60 DEG C dry 1 hour in drying baker；
(4) (3) step gained sample is positioned in deionized water flushing 30 seconds；
(5) (4) step gained sample is positioned over 60 DEG C dry 1 hour in drying baker；
(6) (5) step gained sample is positioned in photoelectron spectrograph detects.
Embodiment 3:
(1) by 316L stainless steel carrier with after deionized water supersound washing, 20 DEG C are soaked in 5MOL/L 1-hydroxy ethylidene-1,1-diphosphonic acid and (depend on
For phosphonic acids, HEDP) in 2 minutes, be positioned in drying baker be dried 1 hour；
(2), after being washed with deionized by (1) step gained stainless steel carrier, it is positioned over 0.25% polyvinyl alcohol (PVA) solution
In, 20 DEG C are soaked 1 hour；
(3) (2) step gained stainless steel carrier is positioned over 60 DEG C dry 1 hour in drying baker；
(4) (3) step gained sample is positioned in deionized water flushing 30 seconds；
(5) (4) step gained sample is positioned over 60 DEG C dry 1 hour in drying baker；
(6) (5) step gained sample is positioned in photoelectron spectrograph detects.
At stainless steel surfaces, polyvinyl alcohol (PVA) ratio test result is:
| Embodiment 1 | 《1% |
| Embodiment 2 | 100% |
| Embodiment 3 | 70% |
Test result illustrate, the embodiment of the present invention 2 employ di 2 ethylhexyl phosphonic acid as chemical binding layer after after, can uniformly coat poly-
Vinyl alcohol (PVA)；Embodiments of the invention 1 are not used then to cannot be carried out coating.And, figure it is seen that new chemistry
The appearance of functional group represents polymer (polyvinyl alcohol) and achieves chemical bond with substrate.
Claims (1)
1. a metal surface film build method for hydrolyzable polymer, comprises the following steps:
(1) by after pending for metal sample deionized water supersound washing, greasy dirt or the corrosion on surface is removed；
After surface is clean, it is positioned over 70 DEG C of dry 5 min in drying baker, or at 20-30 DEG C of air drying 1-2h, with surface
Noresidue water droplet is qualified；Sample is soaked in 20-30 DEG C, with deionized water configuration 2-3mol/L diphosphonic acid solution in 2-5
Minute, carry out 1-hydroxy ethylidene-1,1-diphosphonic acid surface chemistry dress and change the preparation of thin film；It is positioned in drying baker 50-70 DEG C after taking-up to be dried
5-10 min, or at 20-30 DEG C of air drying 2-4h, allows the film drying molding of preparation；Treat that sample surfaces is without obvious liquid
Or colloid, with deionized water lavage specimens product surface 1-3 min, rinse out unnecessary 1-hydroxy ethylidene-1,1-diphosphonic acid crystallization residual, remaining
It is difficult to the 1-hydroxy ethylidene-1,1-diphosphonic acid metal surface chemical conversion film being rinsed；
(2) prepare 0.25-1%'s with the water-soluble poval (PVA) of average molar mass 30000-70000 and deionized water
PVA solution, is positioned over gained metal sample in step (1) in this polyvinyl alcohol (PVA) solution in 20-30 DEG C, 20-30 DEG C of leaching
Bubble 1-2h, makes polyvinyl alcohol homogeneous film formation on the chemical conversion film of 1-hydroxy ethylidene-1,1-diphosphonic acid metal surface；
(3) step (2) gained metal sample is positioned over 60 DEG C dry 1 hour in drying baker；
(4) step (3) gained sample is positioned in deionized water flushing 30 seconds, is positioned over 50-70 DEG C of dry 5-in drying baker
10 min, or at 20-30 DEG C of air drying 2-4h, allow the film drying molding of preparation；
(5) step (4) gained sample is positioned in photoelectron spectrograph detects.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610553970.3A CN106167897A (en) | 2016-08-28 | 2016-08-28 | A kind of metal surface film build method of hydrolyzable polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610553970.3A CN106167897A (en) | 2016-08-28 | 2016-08-28 | A kind of metal surface film build method of hydrolyzable polymer |
Publications (1)
| Publication Number | Publication Date |
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| CN106167897A true CN106167897A (en) | 2016-11-30 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201610553970.3A Pending CN106167897A (en) | 2016-08-28 | 2016-08-28 | A kind of metal surface film build method of hydrolyzable polymer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106282999A (en) * | 2016-08-31 | 2017-01-04 | 济南御麟化工科技有限公司 | A kind of metal surface waterborne polymeric coating production and modified metal material |
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|---|---|---|---|---|
| JP2001329377A (en) * | 2000-05-17 | 2001-11-27 | Kansai Paint Co Ltd | Hydrophilized composition for heat exchanger fin material |
| US6436475B1 (en) * | 1996-12-28 | 2002-08-20 | Chemetall Gmbh | Process of treating metallic surfaces |
| CN101161861A (en) * | 2007-11-22 | 2008-04-16 | 东北大学 | Non-chromium deactivation liquid for processing aluminium alloy and method of use thereof |
| CN101580618A (en) * | 2009-06-24 | 2009-11-18 | 宜兴市高拓高分子材料有限公司 | Polyvinyl alcohol film and preparation method thereof |
| US20120288705A1 (en) * | 2010-11-08 | 2012-11-15 | The Board Of Regents For Oklahoma State University | Hydroxyapatite coated metal surface and method for producing |
| CN102844179A (en) * | 2010-02-15 | 2012-12-26 | 日本帕卡濑精株式会社 | Aluminum or aluminum alloy material having surface treatment coating film, and surface treatment method therefor |
-
2016
- 2016-08-28 CN CN201610553970.3A patent/CN106167897A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6436475B1 (en) * | 1996-12-28 | 2002-08-20 | Chemetall Gmbh | Process of treating metallic surfaces |
| JP2001329377A (en) * | 2000-05-17 | 2001-11-27 | Kansai Paint Co Ltd | Hydrophilized composition for heat exchanger fin material |
| CN101161861A (en) * | 2007-11-22 | 2008-04-16 | 东北大学 | Non-chromium deactivation liquid for processing aluminium alloy and method of use thereof |
| CN101580618A (en) * | 2009-06-24 | 2009-11-18 | 宜兴市高拓高分子材料有限公司 | Polyvinyl alcohol film and preparation method thereof |
| CN102844179A (en) * | 2010-02-15 | 2012-12-26 | 日本帕卡濑精株式会社 | Aluminum or aluminum alloy material having surface treatment coating film, and surface treatment method therefor |
| US20120288705A1 (en) * | 2010-11-08 | 2012-11-15 | The Board Of Regents For Oklahoma State University | Hydroxyapatite coated metal surface and method for producing |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106282999A (en) * | 2016-08-31 | 2017-01-04 | 济南御麟化工科技有限公司 | A kind of metal surface waterborne polymeric coating production and modified metal material |
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| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161130 |
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| RJ01 | Rejection of invention patent application after publication |