CN106756965A - A kind of chromium-free water-based brass antioxidant for adding shitosan and preparation method thereof - Google Patents
A kind of chromium-free water-based brass antioxidant for adding shitosan and preparation method thereof Download PDFInfo
- Publication number
- CN106756965A CN106756965A CN201611157461.5A CN201611157461A CN106756965A CN 106756965 A CN106756965 A CN 106756965A CN 201611157461 A CN201611157461 A CN 201611157461A CN 106756965 A CN106756965 A CN 106756965A
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- Prior art keywords
- antioxidant
- phytic acid
- shitosan
- water
- hours
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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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/52—Treatment of copper or alloys based thereon
-
- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses a kind of chromium-free water-based brass antioxidant for adding shitosan, every liter of antioxidant is made from the following raw materials in parts by weight:50wt.% phytic acid 13 15, 30wt.% hydrogen peroxide 26 28, polyethylene glycol 14 16, glycerine 57, molybdenum bisuphide 12, boron mud 34, acrylic emulsion 78, cocoanut fatty acid diethanolamide 1.7 1.9, isobutyl triethoxy silane 2.4 2.6, shitosan 46, zinc acetate 56, appropriate deionized water, the present invention is with phytic acid, hydrogen peroxide is main component, by phytic acid carry out it is silane coupler modified after, boron mud and other compositions of the compatibility after chitin modified again, obtained antioxidant can be directly dissolved in water, it is easy to operate, low cost, it is not necessary to special installation, product is coated in brass surfaces adhesive force good difficult for drop-off, the anti-corrosion time is long, wearability is good.
Description
Technical field
The present invention relates to metal oxidation resistance technical field, more particularly to a kind of chromium-free water-based brass antioxygen for adding shitosan
Agent and preparation method thereof.
Background technology
The alloy that brass is made up of copper and zinc, both with excellent conductive, thermal conductivity and easily processed into type excellent
Point, and with enough mechanical strengths, hardness and chemical resistance, be commonly used for manufacture valve, water pipe, air-conditioning internal-external machine and connect
Adapter and radiator etc..But run into acid, alkaline corrosion medium or in higher temperatures and high humidity environment be still susceptible to oxygen
Change corrosion and change colour, have a strong impact on outward appearance and use value while also bringing bad influence to secondary operation.It is domestic at present
The outer handling process to copper and its anti-oxidant discoloration of alloy surface mainly has:It is inorganic passivation technique for filming, organic inhibition technology, dilute
Native addition method, self-assembling technique and resinous coat technology etc., wherein most economical, easy method is passivated in brass surfaces
Treatment.Most ripe method is to use bichromate Passivation Treatment, but the sexavalence that the method is remained in process of production and in waste liquid
Chromium is noxious material, and many countries have prohibitted the use of bichromate Passivation Treatment, therefore, document《Brass surfaces richness phytic acid is blunt
Change technical study》With phytic acid, hydrogen peroxide, polyethylene glycol etc. for passivating solution prepared by primary raw material has for brass surfaces antirust
Important realistic meaning.
Treatment is passivated to cold rolling HAl72-2.5-1 brass strips using passivating solution in document, is as a result shown, rich phytic acid
The optimum process condition of passivating film is:Passivation temperature scope is 35~40 DEG C, and pH value is 2.5, and passivation time is 60s;SEM is microcosmic
Pattern shows that film surface is smooth, compact structure;Zero-G test result shows can be to alloy material using rich phytic acid Passivation Treatment
Play a very good protection;Bichromate is used using the sample ratio that rich phytic acid is processed by the saline fog method experiment display of 12h
The sample for the treatment of is free of chromium in having more preferable anti-tarnishing ability and rich phytic acid passivating solution, and pollution of chromium will not be produced in waste liquid.
But the phytic acid film in document, under the heavier environment of humidity, because damp moisture resistance is not good, storage time is short, coating
When brass surfaces carry out secondary operation, resistance to elevated temperatures is limited, in welding process, it is impossible to keep for a long time and multiple
High temperature impact;Secondly in document also there is short anti oxidation time, environmentally friendly bad adaptability, unitary function, heat surely in obtained passivator
The problems such as qualitative difference, weatherability difference and sun-proof ultraviolet radiation preventing difference, thus limit the lifting of overall performance and apply model
Enclose, it is necessary to improve existing production technology and formula, prepare the brass table with the function such as anti-corrosion, anti-oxidant, wear-resisting, sun-proof
Face treatment antioxidant.
The content of the invention
The object of the invention is exactly to make up the defect of prior art, there is provided a kind of chromium-free water-based brass of addition shitosan
Antioxidant and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of chromium-free water-based brass antioxidant for adding shitosan, every liter of antioxidant is made from the following raw materials in parts by weight:
50wt.% phytic acid 13-15,30wt.% hydrogen peroxide 26-28, polyethylene glycol 14-16, glycerine 5-7, molybdenum bisuphide 1-2, boron mud 3-
4th, acrylic emulsion 7-8, cocoanut fatty acid diethanolamide 1.7-1.9, isobutyl triethoxy silane 2.4-2.6, shell gather
Sugared 4-6, zinc acetate 5-6, appropriate deionized water.
A kind of preparation method of the chromium-free water-based brass antioxidant of described addition shitosan, comprises the following steps:
(1)Boron mud is mixed the suspension for being configured to that mass percent concentration is 5-10% in deionized water, 40-60 DEG C is put into
In water-bath, add shitosan ultrasonic disperse to grind 6-12 hours, add acrylic emulsion ultrasound wave irradiation to react 2-8 hours, cooling
To room temperature, the boron mud that must be modified is spray-dried;
(2)Isobutyl triethoxy silane and deionized water are pressed 1:3 mass ratio is warming up to 80- after mixing is stirred at room temperature
100 DEG C, add cocoanut fatty acid diethanolamide, glycerine ultrasonic disperse 5-7 hours, be cooled to 45-55 DEG C of addition phytic acid
Reaction 1-2 hours, obtains modified phytic acid;
(3)By step(1)Obtained modified boron mud grinding distribution is in step(2)In the obtained modified phytic acid aqueous solution, it is warming up to
70-80 DEG C adds molybdenum bisuphide stirring reaction 4-6 hours, cooling;
(4)By step(3)Material is put into reactor, adds zinc acetate and other residual components to stir and evenly mix, and adds water to 1L, in
40-50 DEG C is stirred 20-60 minutes, discharging.
It is an advantage of the invention that:The present invention with phytic acid, hydrogen peroxide as main component, due to there is 24 oxygen originals in phytate molecule
Son, 12 hydroxyls and 6 are phosphate-based, and these atoms or group can form complex compound with metallic atom and metal ion, will plant
Acid carry out it is silane coupler modified after, on the one hand can be anti-by hydrogen bond or dehydration between unreacted phosphorus hydroxyl in passivating process
Should, connection forms spatial networks phytic acid (salt) passivating film of high crosslink density, on the other hand can with silane hydrolyzate after generate-
Si-OH- reaction generation-P-O-Si- keys, can be attached to one layer of metal surface formation colourless with the chelate of metal generation stabilization
Homogeneous, the non-microcracked protective film of transparent, surfacing, thickness densification effectively prevents corrosive medium from penetrating into metal surface,
So as to slow down corrosion of metal, boron mud is added in raw material after chitin modified, then other effective auxiliary agents of compatibility are prepared
Antioxidant can be directly dissolved in water, it is easy to operate, be not necessary to special installation, it is good not that product is coated in into brass surfaces adhesive force
Easy to fall off, the anti-corrosion time is long, wearability is good.
Specific embodiment
It is a kind of add shitosan chromium-free water-based brass antioxidant, every liter of antioxidant by following weight portion raw material system
Into:50wt.% phytic acid 13,30wt.% hydrogen peroxide 26, polyethylene glycol 14, glycerine 5, molybdenum bisuphide 1, boron mud 3, acrylic emulsion
7th, cocoanut fatty acid diethanolamide 1.7, isobutyl triethoxy silane 2.4, shitosan 4, zinc acetate 5, deionized water are fitted
Amount.
A kind of preparation method of the chromium-free water-based brass antioxidant of described addition shitosan, comprises the following steps:
(1)Boron mud is mixed the suspension for being configured to that mass percent concentration is 5-10% in deionized water, 40-60 DEG C is put into
In water-bath, add shitosan ultrasonic disperse to grind 6-12 hours, add acrylic emulsion ultrasound wave irradiation to react 2-8 hours, cooling
To room temperature, the boron mud that must be modified is spray-dried;
(2)Isobutyl triethoxy silane and deionized water are pressed 1:3 mass ratio is warming up to 80- after mixing is stirred at room temperature
100 DEG C, add cocoanut fatty acid diethanolamide, glycerine ultrasonic disperse 5-7 hours, be cooled to 45-55 DEG C of addition phytic acid
Reaction 1-2 hours, obtains modified phytic acid;
(3)By step(1)Obtained modified boron mud grinding distribution is in step(2)In the obtained modified phytic acid aqueous solution, it is warming up to
70-80 DEG C adds molybdenum bisuphide stirring reaction 4-6 hours, cooling;
(4)By step(3)Material is put into reactor, adds zinc acetate and other residual components to stir and evenly mix, and adds water to 1L, in
40-50 DEG C is stirred 20-60 minutes, discharging.
There is following technical parameter using copper antioxidant obtained in the present invention:
(1)Resistance to neutral salt spray corrosion test:By the brass of antioxidant of the present invention treatment, its anti-tarnishing ability is significantly improved, and 8
After h sample remain to keep alloy primary colors there is no Staining, after 12 h, specimen surface remain to keep alloy primary colors, it is only few
The Staining of amount;
(2)The corrosion resistant time of the sample drop of resistance to nitric acid reaches most when sample is put into Passivation Treatment in product of the present invention 60 seconds
Big value 13 seconds.
Claims (2)
1. it is a kind of add shitosan chromium-free water-based brass antioxidant, it is characterised in that every liter of antioxidant is by following weight
The raw material of part is made:50wt.% phytic acid 13-15,30wt.% hydrogen peroxide 26-28, polyethylene glycol 14-16, glycerine 5-7, curing
Molybdenum 1-2, boron mud 3-4, acrylic emulsion 7-8, cocoanut fatty acid diethanolamide 1.7-1.9, isobutyl triethoxy silane
2.4-2.6, shitosan 4-6, zinc acetate 5-6, appropriate deionized water.
2. the preparation method of a kind of chromium-free water-based brass antioxidant for adding shitosan according to claim 1, it is special
Levy is to comprise the following steps:
(1)Boron mud is mixed the suspension for being configured to that mass percent concentration is 5-10% in deionized water, 40-60 DEG C is put into
In water-bath, add shitosan ultrasonic disperse to grind 6-12 hours, add acrylic emulsion ultrasound wave irradiation to react 2-8 hours, cooling
To room temperature, the boron mud that must be modified is spray-dried;
(2)Isobutyl triethoxy silane and deionized water are pressed 1:3 mass ratio is warming up to 80- after mixing is stirred at room temperature
100 DEG C, add cocoanut fatty acid diethanolamide, glycerine ultrasonic disperse 5-7 hours, be cooled to 45-55 DEG C of addition phytic acid
Reaction 1-2 hours, obtains modified phytic acid;
(3)By step(1)Obtained modified boron mud grinding distribution is in step(2)In the obtained modified phytic acid aqueous solution, it is warming up to
70-80 DEG C adds molybdenum bisuphide stirring reaction 4-6 hours, cooling;
(4)By step(3)Material is put into reactor, adds zinc acetate and other residual components to stir and evenly mix, and adds water to 1L, in
40-50 DEG C is stirred 20-60 minutes, discharging.
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CN201611157461.5A CN106756965A (en) | 2016-12-15 | 2016-12-15 | A kind of chromium-free water-based brass antioxidant for adding shitosan and preparation method thereof |
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CN201611157461.5A CN106756965A (en) | 2016-12-15 | 2016-12-15 | A kind of chromium-free water-based brass antioxidant for adding shitosan and preparation method thereof |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102534595A (en) * | 2011-12-28 | 2012-07-04 | 蚌埠市钰诚五金工贸有限公司 | Preparation process of metal surface protective treatment fluid |
CN105177559A (en) * | 2015-09-16 | 2015-12-23 | 马鞍山杰创塑胶科技有限公司 | Salt-spray-resistant aluminum profile rare earth silane processing liquid and preparation method thereof |
CN105951088A (en) * | 2016-06-27 | 2016-09-21 | 无锡伊佩克科技有限公司 | Low-chromium high-corrosion-resistance passivation solution and preparation method thereof |
-
2016
- 2016-12-15 CN CN201611157461.5A patent/CN106756965A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102534595A (en) * | 2011-12-28 | 2012-07-04 | 蚌埠市钰诚五金工贸有限公司 | Preparation process of metal surface protective treatment fluid |
CN105177559A (en) * | 2015-09-16 | 2015-12-23 | 马鞍山杰创塑胶科技有限公司 | Salt-spray-resistant aluminum profile rare earth silane processing liquid and preparation method thereof |
CN105951088A (en) * | 2016-06-27 | 2016-09-21 | 无锡伊佩克科技有限公司 | Low-chromium high-corrosion-resistance passivation solution and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
蔡薇等: ""黄铜表面富植酸钝化工艺研究"", 《稀有金属》 * |
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