CN103726056B - The protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal - Google Patents
The protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal Download PDFInfo
- Publication number
- CN103726056B CN103726056B CN201310738118.XA CN201310738118A CN103726056B CN 103726056 B CN103726056 B CN 103726056B CN 201310738118 A CN201310738118 A CN 201310738118A CN 103726056 B CN103726056 B CN 103726056B
- Authority
- CN
- China
- Prior art keywords
- water
- agent
- metal
- shaped metal
- soluble molecules
- 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.)
- Active
Links
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Paints Or Removers (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The water of 0.5 ~ 1.5:10 of the invention discloses the protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal, the steps include: A, by mass ratio be mixes with organic solvent, stirs, makes mixed solvent; B, add steps A mixed solvent quality 30 ~ 50% emulsifying agent, stir, make mixture; C, add step B gained mixture quality 12 ~ 20% film, stir, obtain mixing solutions further; D, the tensio-active agent of 1.5 ~ 2.0% adding step C gained mixing solutions quality and the reductive agent of 0.1 ~ 0.5%; heat under 51 ~ 58 DEG C of water bath condition; control mixing solutions temperature, continue stirring 90 ~ 150 minutes, obtain water soluble molecules self-assembled film shaped metal protective material.Present invention process is simple, and energy consumption is low, environmental friendliness, and protective material can form molecular self-assembled monolayer in metallic surface, effectively protects metal nondiscoloration.Present invention process is simple, be easy to accomplish scale production.
Description
Technical field
The present invention relates to metal protection agent field, be specifically related to the protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal.A kind of water soluble molecules self-assembled film shaped metal protective material prepared by this technology can be used for the rust protection protection etc. of various electroplating technology device metal coating, various metallic cultural relics.
Background technology
The resistivity of common platinum, gold and silver, nickel, copper, aluminium is respectively 10.6,2.4,1.58,6.8,1.67,2.66 μ Ω cm, and the thermal conductivity of these platinum, gold and silver, nickel, copper, aluminium is then respectively 0.72,3.17,4.29,0.91,4.01,2.37 Wcm
-1k
-1, as can be seen here, aggregate resistance rate and thermal conductivity ratio comparatively, the conduction thermal resistance better performances of gold and silver.In addition, gold and silver also have many excellent characteristics, and as silver also has high reflective, its reflectivity is up to 95%, and gold and silver have higher chemical stability, and weldability and ductility are also splendid.Based on these excellent Wuli-Shili-Renli system approach of gold and silver, gold and silver are in electronic industry, signal equipment, instrument, aircraft, opticinstrument, high-frequency component and waveguide, and the aspect such as ornament, decoration is widely applied.But gold and silver are as precious metal, its application cost is higher, therefore generally takes, at good base metal (as copper) the surperficial plating one deck silver metal of conductivity, so not only to make it have the premium properties of gold and silver, and saves cost.In recent years, in the space flight and aviation electronic instrument and meters such as navigation, control, communication and equipment, gold and silver electroplating device obtains and applies widely.
Although with many metallographic phase ratios, the chemical stability of gold and silver, nickel is good, has stronger corrosion resistance, use, store and all can get rusty in transportation variable color.If silver features and silvering long-term exposure are in malaria, to be subject in air various volatile sulfur compounds (as H
2s, CS
2, OCS), oxide compound (SO
2, NO
xdeng), (muriate in air is mainly derived from the atomization of burning of coal, waste incineration, volcanicity, sewage disposal, sea salt and seawater, and the photo-chemical smog etc. of atmospheric polluting material for oxygen, ozone and halogenide; Indoor muriate is mainly caused by industrial cleaning agent, refrigeration agent and plastics etc. slow decomposition.) etc. corrosion, make the obfuscation variable color of silver features surface, not only affect the appearance luster reduction decorate properties of silverware or silver plated item, and more seriously affect welding property and the electrical specification of electronic product silver plate.Research shows that variable color makes silvered film surface resistivity increase about 20 ~ 80%, and electric energy loss increases, thus make the stability of electronics, reliability greatly reduces, and even causes major accident.Therefore, no matter be as functional material, or the silver plate of decorative use, all have to pass through Anti-tarnishing process after plating, to improve its corrosion resistance.
Under prior art condition, prevent the major technique of burning variable color from having: Anti-tarnishing alloy (as yellow gold, Stainless Steel Alloy etc.), employing plating or ion sputtering are at other metal of metallic surface plating (nickel layer, silvered film and platinum plating layer, Gold plated Layer etc.), chemical passivation (K
2cr
2o
7-Glacial acetic acid, two blunt method and K
2cr
2o
7-nitric acid Passivation Treatment), electrochemical passivation, galvanic couple passivation (negative electrode or anodic protection etc.), deposited oxide film, metallic surface rust protection coating treatment technology (as organic adsorption passivation layer, resin coating, plasma polymerization film, self-assembled film etc.), compound organic discoloration inhibitors etc. (Yang Changjiang. gold and silver coin Discoloration mechanism and anti-discolouring technology research [D]. Dalian University of Technology Ph.D. Dissertation, 2008).For the resist technology of silvering, the Anti-tarnishing technique comparatively early adopted is electrophoresis beryllium hydroxide.Although the anti-silver tarnish effect of this technology is better, because processing condition are comparatively harsh, be therefore difficult to apply in the industrial production.Also been proposed the Anti-tarnishing technique being coated with organic oil film subsequently; the organism of coating comprises benzene wax silicon solution, paraffin-toluene solution, Vaseline-toluene solution; though this technique can protect silver to a certain extent not by the corrosion of Atmospheric Sulfur compound, this kind of oiliness film is easily stained with ash and space is many.Then rosin-toluene proofing liquid, epoxy resin-polystyrene-ceresine-rosin is adopted to merge the inhibiter configured at organic solvent solutions such as toluene, the effect of the anti-silver tarnish of this type of film is better, but contact electricity performance, solderability decline (Li Hanye. the research [D] of copper base plating silver layer Anti-tarnishing. Northeastern University's master thesis, 2005).In addition, as previously mentioned, at the metal of silvered film electroplating surface more inertia, as germanium, platinum or gold etc., inert metal alloy approach prevents silver tarnish effect better, little on impacts such as plating piece electric property, decoration and performances attractive in appearance, but the composition of alloy has very strict requirement, the manufacturing process of alloy is also very complicated, raw materials cost and manufacturing technology cost all higher, only requiring higher key part is just adopted, be difficult to adapt to large-scale industrial application.
Along with the development of related industries technology and the world, the domestic pay attention to day by day to environment protection, in the decades in future, comprise heavy metal ion (as Cr
3+, CrO
4 2-deng) surface treatment agent progressively will limit and use and be progressively eliminated, and the usage quantity of the environmentally friendly metal conditioner of new type water-solubility, protective material etc. will significantly increase.At present, the product in China's Mainland water-soluble metal protective material market is main primarily of the areas such as TaiWan, China, Singapore, Japan, Germany and national company.And the use of the water-soluble protective material product of American-European Main Developed Countries reaches more than 85%, China's Mainland electronics industry, metal protection field, electroplating industry field etc., the protectant ratio of the water-soluble metal used is less than 40%.Visible China's Mainland water-soluble metal Anti-tarnishing protective material market potential is huge.
Correlative study and the disclosed patented technology of the resist technology of domestic and international metal protective material, anti-silver tarnish and preventing metal corrosion etc. occur in a large number.The Chinese patent of patent No. ZL200710075422.5 discloses " a kind of water-soluble silver protecting agent and preparation method thereof ", disclosed in this patent, technology is silver protecting agent: the linear saturated alkane mercaptan utilizing carbochain to be 12-24, and carbochain is no more than oligopolymer wetting agent and the emulsifying agent composition of the hydroxyl functional group of 12; Its preparation method is, is being not less than at 60 DEG C of temperature, by linear saturated alkane mercaptan, wetting agent with emulsifying agent is fully emulsified, Homogeneous phase mixing.The Chinese patent of number of patent application 201010193567.7 also discloses one " electric-contact metal protectant "; this invention technology relates to a kind of surface protectant being mainly used in electronic devices and components and preparation method thereof; have the filmogen of 3.0 ~ 8.0%, 2.5 ~ 5.0% organic inhibitor, the soldering flux of 1.5 ~ 3.0%, the lubricant of 2.5 ~ 5.0%; surplus is solvent, makes after mixing, heating.The Chinese patent of number of patent application 201010535197.0 also discloses " a kind of anti-silver tarnish material and its preparation method and application ", and this material molecule structural formula is expressed as II, and the R in molecular formula for be in ortho position, a position or contraposition on phenyl ring, and R is expressed as C
nh
2n+1-group, n=0 ~ 8, n is integer.The preparation method of this anti-silver tarnish material of this disclosure of the invention and application.This application specification sheets claims: this material discoloration-resisting prepared by invention technology is good, can ensure ag material pliability well again simultaneously, is applicable to application with pregnant woman's radioprotective clothes; Overall synthesis technique is simple, only needs single step reaction and flash liberation; Coating processes can be various, by directly making from solution spin coating, also can spray.The Chinese patent of number of patent application 201210389716.0 discloses " a kind of Steel/cast iron metal protective agent and preparation method thereof ", and the disclosure technology adopts weight proportion to be respectively phytic acid 6-20%; Organic phosphates corrosion inhibiting and descaling agent 10-35%; High molecular polymer 0.5-2%; Aluminum orthophoshpate, zinc hydrate 2.5-6%; 5-nitro isophthalic ester zinc 0.1-0.5%; Water surplus; Preparation method is: added by water in reactor, add phytic acid, organic phosphates corrosion inhibiting and descaling agent, high molecular polymer stir, under agitation add aluminum orthophoshpate, zinc hydrate and 5-nitro isophthalic ester zinc and stir to dissolve completely to material for 60-120 minute and form.The Chinese patent of number of patent application 201310212527.6 discloses " a kind of part aqueous metal protection agent and production technique thereof ", it comprises monomer, molecular weight adjusting agent and initiator, described monomer comprises the methyl methacrylate that massfraction is 20%-40%, massfraction is the butyl acrylate of 20%-40%, massfraction is the vinylformic acid of 10%-18%, massfraction is the vinylbenzene of 5%-15% and massfraction is the Hydroxyethyl acrylate of 8%-15%, the amount that described molecular weight adjusting agent is added is the 0.1%-2% of described monomer total mass, the amount that described initiator adds is the 0.1%-5% of described monomer total mass.In addition, No. 4948523, the U.S. patent discloses " a kind of composition without chlorine silver protecting lubricants ", and silver protecting agent disclosed in this technology is by phosphorodithioic acid dialkyl ester salt compound, the C of zinc
5~ C
60carboxylic acid and (1) guanidine, urea and thiourea compound; (2) to C
1~ C
20alkyl or the hydrocarbyl monoamine that replaces of hydroxyl, at least one in the polyalkylene polyamine of Alkylenediamine and (3) and N-alkyl glycine is prepared from.
There is obvious defect in existing metal protection and silver protecting agent technology:
First; although alloy technology has good effect to metal protection and Anti-tarnishing etc.; but the composition of alloy has very strict requirement; the manufacturing process of alloy is also very complicated; raw materials cost and manufacturing technology cost all higher; only requiring higher key part is just adopted, difficulty is suitable for large-scale industrial application.
Second; electroplating technology is the same with alloy technology; metal variable color and rust-proof effect is prevented preferably although have; but electroplating technical conditions is comparatively harsh; process specifications is higher, is obviously restricted, also needs additionally to use corresponding resist technology after plating in the application of the related fields such as metallic cultural relics protection and decoration, jewel; therefore, the practical application of electroplating technology is subject to larger restriction equally.
3rd, the chemical processing agent that the technology etc. such as chemical passivation, galvanic couple passivation use or there is heavy metal ion (Cr
3+, CrO
4 2-deng) to problems such as the pollutions of environment, exist the consumption of electric energy and the process technology limit of electrochemical techniques, use procedure always may produce more waste, pollutent and toxic product or consume the defect such as the more energy or Technology requirement harshness itself.
4th; existing metallic surface rust protection coating treatment technology (as organic adsorption passivation layer, resin coating, plasma polymerization film etc.); have that operation is complicated or use range is not extensive; manufacture protectant synthesis cycle longer; or complex process, produce starting material and production technology cost higher, or use procedure produces environmental pollution or not obvious etc. to the protected effect of metal; both be difficult to be widely used, and be also comparatively difficult to realize large-scale industrial and produce.
5th, the protectant preparation of existing water-soluble metal and production technology process, owing to have employed complicated chemical reaction or molecular weight is comparatively large or fusing point is higher starting material, there is preparation, reaction process complexity or operation complicated (Chinese patent as application number 201310212527.6 comprises 7 ~ 8 or more more complicated preparation processes), temperature of reaction equally, higher (Chinese patent as patent No. ZL200710075422.5 prepares the control temperature of the Technology of water-soluble silver protecting agent for being not less than 60 DEG C (referring to its specification digest); The reaction reflux temperature of the Chinese patent technology of application number 201310212527.6 is 85 ~ 90 DEG C, 100 ~ 103 DEG C) etc. deficiency, directly making to prepare the requirement of protective material instrument and supplies improves, and energy consumption is high, undoubtedly manufacturing cost, use cost can directly improve.
6th, the scope that the protectant protected effect of existing water-soluble metal is undesirable, protective material is suitable for is not extensive yet.Protective material prepared by the Chinese patent technology as patent No. ZL200710075422.5 to be " a kind of water-soluble silver protecting agent " and application number be 201010535197.0 the protective material prepared of Chinese patent technology be " a kind of anti-silver tarnish material and its preparation method and application ", the Anti-tarnishing namely only limited the use of in silver is protected; The Chinese patent protective material disclosed prepared by " a kind of Steel/cast iron metal protective agent and preparation method thereof " of application number 201210389716.0 is only applicable to the corrosion protection of iron and steel and cast iron.
In addition; the technology of the Chinese patent disclosed a kind of " electric-contact metal protectant " of number of patent application 201010193567.7; relate to a kind of surface protectant being mainly used in electronic devices and components and preparation method thereof; have the filmogen of 3.0 ~ 8.0%, 2.5 ~ 5.0% organic inhibitor, the soldering flux of 1.5 ~ 3.0%, the lubricant of 2.5 ~ 5.0%; surplus is solvent, makes after mixing, heating.The obvious raw material type of this invention technology is more, technique is comparatively complicated, and production technology cost is obviously higher, and its protective material is also only applicable to the protection of electronic devices and components, the obvious scope of application extensive, and its defect and deficiency are apparent.
Summary of the invention
In order to solve the deficiency existing for existing metal protection agent and technology of preparing thereof, the object of the invention is to there are provided the protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal.Present invention process flow process is simple, and due to used raw material be the lower low polymerization degree organism of fusing point or more micromolecular organism, the consistency between raw material thing is good, preparation process temperature controls lower, without special equipment requirements, with short production cycle while energy consumption is low, production efficiency is high; The advantages of nontoxic raw materials that protective material prepared by the technology of the present invention is used or low toxicity; The metal protection agent good water solubility of preparation, operation flow process is simple; Applied widely, be applicable to the protection of various types of metal products, metal plating and metal device.The technology of the present invention can be easy to accomplish scale production.
In order to realize above-mentioned object, the present invention is by being achieved with following technical proposals:
The protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal, the steps include:
A, be that the water of 0.5 ~ 1.5:10 mixes with organic solvent by mass ratio, stir, make mixed solvent;
B, add steps A mixed solvent quality 30 ~ 50% emulsifying agent, stir, make mixture;
C, add step B gained mixture quality 12 ~ 20% film 8,14-dihydroxyl Stearyl mercaptan (D-SM), stir, obtain mixing solutions further;
D, add step C gained mixing solutions quality 1.5 ~ 2.0% tensio-active agent and 0.1 ~ 0.5% reductive agent technical pure vitamins C (or claim xitix; be called for short: VC or AA); heat under 51 ~ 58 DEG C of water bath condition; continue stirring 90 ~ 150 minutes, obtain water-soluble metal protective material.
Described organic solvent is α-phenyl methyl-ω-[(1,1,3,3-tetramethyl butyl) phenoxy group]-poly-(oxygen-ethylene) (TRITON);
Described emulsifying agent is hydroxyethyl lipid acid third fat (HDP);
Described membrane-forming agent is 8,14-dihydroxyl Stearyl mercaptan (D-SM);
Described reductive agent is that (i.e. xitix, is called for short: VC or AA) technical pure vitamins C;
Described tensio-active agent is sodium lauryl sulphate (SDS).
Described water is the one in deionized water, distilled water, tap water or natural water.
The protectant physico-chemical property of water soluble molecules self-assembled film shaped metal prepared by the technology of the present invention is: be semi-solid state liquid (paraffin shape) under room temperature (25 ~ 28 DEG C) condition, without definite melting point; It is light yellow or tea yellow liquid at 30 ~ 45 DEG C; Density is a bit larger tham water, is about 1.022g/mL; There is light thiol smell; Can mix with arbitrary proportion with water under 40 DEG C and above temperature condition.
Adopt technical scheme of the present invention, following significant effect can be obtained:
First; water-soluble metal protective material prepared by the technology of the present invention method; due in the solution between membrane-forming agent and surfactant molecule; form cryptomere molecular self-assembly; just naturally can open in metallic surface in the cryptomere molecular self-assembling body short period of time (several seconds); and again form self-assembled monolayer in metallic surface, effectively can contact with the direct of oxidizing gas by isolating metal, make metal Coloring Time be able to effective prolongation.The sulphide discoloration test in the potassium sulfide solution of 2% of the argent protected with protective material of the present invention and silver-plated testpieces shows; under room temperature (25 ~ 28 DEG C) condition, Coloring Time is all more than 8 minutes, reaches most 78 points 47 seconds (referring to the embodiment 3 of the embodiment of present specification).
The second, the membrane-forming agent that the present invention is used is 8; 14-dihydroxyl Stearyl mercaptan; except the sulfydryl of mercaptan and metal form coordinate bond and film forming is protected metal and oxidizing gas and isolated; due to also may hydrogen bond be formed between hydroxyl; make molecular self-assembled monolayer more firm; further enhance the protective value of self-assembled film to metal, significant prolongation is to the guard time (referring to following table 1) of metal.
The present invention uses 8, a kind of water soluble molecules self-assembled film shaped metal protective material S1(of 14-dihydroxyl Stearyl mercaptan prepared by film (being called for short " 8,14-mercaptan " in table 1) show in t
s1) with use Stearyl mercaptan (being called for short " mercaptan " in table 1) a kind of water-soluble silver protecting agent S2(of preparing to show in t
s2the Chinese patent that referenced patent number is ZL200710075422.5 prepares the method preparation of water-soluble silver protecting agent; refer to its specification sheets and embodiment); the two (S1, S2) is to the protected effect test of part metals tested by the present invention; the part preferred result contrast of sulfuration test (under room temperature 25 ~ 28 DEG C of conditions) namely in the potassium sulfide solution of 2%, as t in following table 1(table
s1and t
s2represent the metal after with protective material S1 and the S2 difference conservation treatment of two kinds of simultaneous tests respectively, the Coloring Time in potassium sulfide solution) shown in:
Table 1
3rd, the water-soluble metal protective material prepared by the present invention, have employed the good xitix reductive agent of reductibility, can reduce most metal ion (as Ag
+, Au
3+, Ni
2+deng), also can form water-soluble complexes with many heavy metal ion, make beavy metal impurity ion water-soluble, make shielded metal device variable color (mainly metal ions M
n+with S
2-, Cl
-, O
2-produce ferrous metal sulfide, dark-coloured halogenide and oxide compound Deng combining) possibility and discoloration greatly reduce, protect metal further, make metal variable color be able to effective alleviation, effectively extend Coloring Time (referring to following table 2).
The present invention uses reductive agent vitamins C (i.e. xitix; VC or AA; test sample A) and do not use reductive agent vitamins C (i.e. xitix; VC or AA; test sample B) prepared by a kind of water soluble molecules self-assembled film shaped metal protective material; to metal protection effect tested by the present invention, the preferred comparing result of part of sulphide discoloration test (under room temperature 25 ~ 28 DEG C of conditions) namely in the potassium sulfide solution of 2%, as the T in following table 2(table 2
aand T
b, represent the metal after with protective material A, B difference conservation treatment of two kinds of simultaneous tests respectively, the Coloring Time in potassium sulfide solution) shown in:
Table 2
Four, the water-soluble metal protective material prepared by the present invention; main raw material used is water-soluble good organism; under general temperature condition, (more than 40 DEG C) almost can mix with arbitrary proportion with water; be easy to the aqueous solution making various concentration; use operational anomaly is simple; can be used for different shape, the metal products of size or the protection of device, applied widely.
5th; due to a kind of water soluble molecules self-assembly shaped metal protective material prepared by the present invention; main raw material used is all fusing point lower than the organic substance (water and reductive agent except) of 55 DEG C; preparation process and use procedure do not need higher temperature; to produce and Energy in use is low, production unit is simple, be easier to realize efficiently, large-scale production.
Accompanying drawing explanation
Fig. 1 is the SEM photo of the molecular self-assembled monolayer that a kind of protective material prepared is formed on silvering surface.
Fig. 2 is the AFM photo of the molecular self-assembled monolayer that a kind of protective material prepared is formed on gold plate surface.
Embodiment
Below in conjunction with embodiment and accompanying drawing, further detailed description is done to the present invention.
embodiment 1:
The protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal, the steps include:
A, be tap water and 10kg organic solvent α-phenyl methyl-ω-[(1 of 0.5:10 and 0.5kg by mass ratio, 1,3,3-tetramethyl butyl) phenoxy group]-poly-(oxygen-1,2-ethylidene) (be called for short TRITON) mix in a kettle., stir 2 minutes, make mixed solvent;
B, add steps A gained mixed solvent quality 30% emulsifying agent, i.e. 3.15kg hydroxyethyl lipid acid third fat (HDP), stirs 3 minutes, makes mixture;
C, add step B gained mixture quality 12% membrane-forming agent, i.e. 1.638kg 8,14-dihydroxyl Stearyl mercaptan (D-SM), stirs 3 minutes, obtains mixing solutions further;
D, add step C gained mixing solutions quality 1.5% tensio-active agent; the i.e. reductive agent of sodium lauryl sulphate (SDS) 0.229kg and 0.1%; i.e. vitamins C (xitix; be called for short VC or AA) 15.3g; heating in water bath; control reactor mixing solutions temperature 51 DEG C, continue stirring 150 minutes, obtain water-soluble metal protective material.
The metal protection agent of the preparation with SEM and AFM technical measurement forms the shape characteristic of molecular self-assembled monolayer on silvering surface.The molecular self-assembled monolayer formed is orderly, fine and close, and thickness is about 20 ~ 35nm(and refers to accompanying drawing 1 and accompanying drawing 2).
The aqueous solution that mass percent concentration is 3% is made into the metal protection agent of protective material protection preparation of the present invention; by argent and silver-plated testpieces dynamic soaking 10 ~ 30 second in the solution; distilled water embathes, air-dry or naturally dry; be immersed in again in the potassium sulfide solution of 2%; the test of record sulphide discoloration; result shows: under room temperature (25 ~ 28 DEG C) condition, Coloring Time was more than 8 minutes, reach most 14 points 23 seconds.
embodiment 2:
The protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal, the steps include:
A, be deionized water and 10kg organic solvent α-phenyl methyl-ω-[(1 of 0.75:10 and 0.75kg by mass ratio, 1,3,3-tetramethyl butyl) phenoxy group]-poly-(oxygen-1,2-ethylidene) (be called for short TRITON) mix in a kettle., stir 3 minutes, make mixed solvent;
B, add steps A gained mixed solvent quality 35% emulsifying agent, i.e. 3.76kg hydroxyethyl lipid acid third fat (HDP), stirs 5 minutes, makes mixture;
C, add step B gained mixture quality 15% membrane-forming agent, i.e. 2.18kg 8,14-dihydroxyl Stearyl mercaptan (D-SM), stirs 4 minutes, obtains mixing solutions further;
D, add step C gained mixing solutions quality 1.65% tensio-active agent; the i.e. reductive agent of sodium lauryl sulphate (SDS) 0.275kg and 0.2%; i.e. vitamins C (xitix; be called for short VC or AA) 33.9g; heating in water bath; control reactor mixing solutions temperature 54 DEG C, continue stirring 140 minutes, obtain water-soluble metal protective material.
The metal protection agent of the preparation with SEM and AFM technical measurement forms the shape characteristic of molecular self-assembled monolayer on silvering surface.The molecular self-assembled monolayer formed is orderly, fine and close, and thickness is about 20 ~ 35nm(and refers to accompanying drawing 1 and accompanying drawing 2).
The aqueous solution that mass percent concentration is 3% is made into the metal protection agent of protective material protection preparation of the present invention; by argent and silver-plated testpieces dynamic soaking 10 ~ 30 second in the solution; distilled water embathes, air-dry or naturally dry; be immersed in again in the potassium sulfide solution of 4%; the test of record sulphide discoloration; result shows: under room temperature (25 ~ 28 DEG C) condition, Coloring Time is all more than 8 minutes, reach most 18 points 47 seconds.
embodiment 3:
The protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal, the steps include:
A, be distilled water and 20kg organic solvent α-phenyl methyl-ω-[(1 of 1.0:10 and 2.0kg by mass ratio, 1,3,3-tetramethyl butyl) phenoxy group]-poly-(oxygen-1,2-ethylidene) (be called for short TRITON) mix in a kettle., stir 3 minutes, make mixed solvent;
B, add steps A gained mixed solvent quality 44.5% emulsifying agent, i.e. 9.79kg hydroxyethyl lipid acid third fat (HDP), stirs 5 minutes, makes mixture;
C, add step B gained mixture quality 15.5% membrane-forming agent, i.e. 4.93kg 8,14-dihydroxyl Stearyl mercaptan (D-SM), stirs 6 minutes, obtains mixing solutions further;
D, add step C gained mixing solutions quality 1.80% tensio-active agent; the i.e. reductive agent of sodium lauryl sulphate (SDS) 0.661kg and 0.3%; i.e. vitamins C (xitix; be called for short VC or AA) 112.1g; heating in water bath; control reactor mixing solutions temperature 55 DEG C, continue stirring 120 minutes, obtain water-soluble metal protective material.
The metal protection agent of the preparation with SEM and AFM technical measurement forms the shape characteristic of molecular self-assembled monolayer on silvering surface.The molecular self-assembled monolayer formed is orderly, fine and close, and thickness is about 20 ~ 35nm(and refers to accompanying drawing 1 and accompanying drawing 2).
The aqueous solution that mass percent concentration is 3% is made into the metal protection agent of protective material protection preparation of the present invention; by argent and silver-plated testpieces dynamic soaking 10 ~ 30 second in the solution; distilled water embathes, air-dry or naturally dry; be immersed in again in the potassium sulfide solution of 2%; the test of record sulphide discoloration; result shows: under room temperature (25 ~ 28 DEG C) condition, Coloring Time was more than 13 minutes, reach most 78 points 47 seconds.
embodiment 4:
The protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal, the steps include:
A, be distilled water and 30kg organic solvent α-phenyl methyl-ω-[(1 of 1.3:10 and 3.9kg by mass ratio, 1,3,3-tetramethyl butyl) phenoxy group]-poly-(oxygen-1,2-ethylidene) (be called for short TRITON) mix in a kettle., stir 4 minutes, make mixed solvent;
B, add steps A gained mixed solvent quality 48% emulsifying agent, i.e. 16.27kg hydroxyethyl lipid acid third fat (HDP), stirs 5 minutes, makes mixture;
C, add step B gained mixture quality 17.5% membrane-forming agent, i.e. 8.78kg 8,14-dihydroxyl Stearyl mercaptan (D-SM), stirs 8 minutes, obtains mixing solutions further;
D, add step C gained mixing solutions quality 1.85% tensio-active agent; the i.e. reductive agent of sodium lauryl sulphate (SDS) 1.091kg and 0.4%; i.e. vitamins C (xitix; be called for short VC or AA) 240g; heating in water bath; control reactor mixing solutions temperature 57 DEG C, continue stirring 130 minutes, obtain water-soluble metal protective material.
The metal protection agent of the preparation with SEM and AFM technical measurement forms the shape characteristic of molecular self-assembled monolayer on silvering surface.The molecular self-assembled monolayer formed is orderly, fine and close, and thickness is about 20 ~ 35nm(and refers to accompanying drawing 1 and accompanying drawing 2).
The aqueous solution that mass percent concentration is 5% is made into the metal protection agent of protective material protection preparation of the present invention; by argent and silver-plated testpieces dynamic soaking 10 ~ 30 second in the solution; distilled water embathes, air-dry or naturally dry; be immersed in again in the potassium sulfide solution of 2%; the test of record sulphide discoloration; result shows: under room temperature (25 ~ 28 DEG C) condition, Coloring Time was more than 8 minutes, reach most 43 points 19 seconds.
embodiment 5:
The protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal, the steps include:
A, be natural water and 40kg organic solvent α-phenyl methyl-ω-[(1 of 1.5:10 and 6kg by mass ratio, 1,3,3-tetramethyl butyl) phenoxy group]-poly-(oxygen-1,2-ethylidene) (be called for short TRITON) mix in a kettle., stir 6 minutes, make mixed solvent;
B, add steps A gained mixed solvent quality 50% emulsifying agent, i.e. 23kg hydroxyethyl lipid acid third fat (HDP), stirs 10 minutes, makes mixture;
C, add step B gained mixture quality 20% membrane-forming agent, i.e. 13.8kg 8,14-dihydroxyl Stearyl mercaptan (D-SM), stirs 10 minutes, obtains mixing solutions further;
D, add the tensio-active agent of the mixing solutions quality 2.0% of step C gained; the i.e. reductive agent of sodium lauryl sulphate (SDS) 1.656kg and 0.5%; i.e. vitamins C (xitix; being called for short VC or AA) 422.3g joins in C gained mixing solutions; heating in water bath; control reactor mixing solutions temperature 58 DEG C, continue stirring 90 minutes, obtain water-soluble metal protective material.
The metal protection agent of the preparation with SEM and AFM technical measurement forms the shape characteristic of molecular self-assembled monolayer on silvering surface.The molecular self-assembled monolayer formed is orderly, fine and close, and thickness is about 20 ~ 35nm(and refers to accompanying drawing 1 and accompanying drawing 2).
The aqueous solution that mass percent concentration is 3% is made into the metal protection agent of protective material protection preparation of the present invention; by argent and silver-plated testpieces dynamic soaking 10 ~ 30 second in the solution; distilled water embathes, air-dry or naturally dry; be immersed in again in the potassium sulfide solution of 2%; the test of record sulphide discoloration; result shows: under room temperature (25 ~ 28 DEG C) condition, Coloring Time was more than 8 minutes, reach most 29 points 57 seconds.
The foregoing is only the good embodiment of the present invention, not in order to limit the present invention, every any amendment, on an equal basis replacement and improvement etc. made within the present invention's spirit and principle, all should be included within the scope of protection of the invention.
Claims (2)
1. the protectant preparation method of water soluble molecules self-assembled film shaped metal, the steps include:
A, be that the water of 0.5 ~ 1.5:10 mixes with organic solvent by mass ratio, stir, make mixed solvent;
B, add steps A mixed solvent quality 30 ~ 50% emulsifying agent, stir, make mixture;
C, add step B gained mixture quality 12 ~ 20% film, stir, obtain mixing solutions further;
D, the tensio-active agent of 1.5 ~ 2.0% adding step C gained mixing solutions quality and the reductive agent of 0.1 ~ 0.5%, heat under 51 ~ 58 DEG C of water bath condition, continues stirring 90 ~ 150 minutes, obtain water soluble molecules self-assembled film shaped metal protective material;
Described organic solvent is α-phenyl methyl-ω-[(1,1,3,3-tetramethyl butyl) phenoxy group]-poly-(oxygen-ethylene);
Described emulsifying agent is hydroxyethyl lipid acid third fat;
Described film is 8,14-dihydroxyl Stearyl mercaptan;
Described tensio-active agent is sodium lauryl sulphate;
Described reductive agent is technical pure vitamins C.
2. the protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal as claimed in claim 1, is characterized in that: described water is the one in deionized water, distilled water, tap water or natural water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310738118.XA CN103726056B (en) | 2013-12-26 | 2013-12-26 | The protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310738118.XA CN103726056B (en) | 2013-12-26 | 2013-12-26 | The protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103726056A CN103726056A (en) | 2014-04-16 |
| CN103726056B true CN103726056B (en) | 2015-10-21 |
Family
ID=50450344
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310738118.XA Active CN103726056B (en) | 2013-12-26 | 2013-12-26 | The protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103726056B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104593795A (en) * | 2015-01-08 | 2015-05-06 | 邯郸学院 | Brightness-retaining agent for silverware |
| CN105063705A (en) * | 2015-07-30 | 2015-11-18 | 柳州市旭平首饰有限公司 | Method for preventing color change of copper ornament plated with silver |
| US20190177859A1 (en) * | 2016-06-23 | 2019-06-13 | Atotech Deutschland Gmbh | A water-based composition for post-treatment of metal surfaces |
| CN111519219A (en) * | 2019-12-21 | 2020-08-11 | 东莞奕创表面处理科技有限公司 | Silver electroplating liquid composite additive and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353800A (en) * | 2007-07-26 | 2009-01-28 | 深圳市华傲创表面技术有限公司 | Water-soluble silver protecting agent and preparation thereof |
| CN102002696A (en) * | 2010-11-01 | 2011-04-06 | 李士法 | Silver tarnishing prevention material, and preparation method and application thereof |
| CN102277576A (en) * | 2010-06-08 | 2011-12-14 | 罗英 | Electric-contact metal protectant |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0576856A (en) * | 1991-04-08 | 1993-03-30 | Mitsubishi Gas Chem Co Inc | Multifunctional water treatment agent |
| JP5680289B2 (en) * | 2009-08-28 | 2015-03-04 | 伯東株式会社 | Water treatment agent and water treatment method |
-
2013
- 2013-12-26 CN CN201310738118.XA patent/CN103726056B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353800A (en) * | 2007-07-26 | 2009-01-28 | 深圳市华傲创表面技术有限公司 | Water-soluble silver protecting agent and preparation thereof |
| CN102277576A (en) * | 2010-06-08 | 2011-12-14 | 罗英 | Electric-contact metal protectant |
| CN102002696A (en) * | 2010-11-01 | 2011-04-06 | 李士法 | Silver tarnishing prevention material, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103726056A (en) | 2014-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Verma et al. | Ionic liquids as green and sustainable corrosion inhibitors for metals and alloys: an overview | |
| CN101532153B (en) | Amorphous nano-alloy plating layer of electrodeposition nickel-based series, electroplating liquid and electroplating process | |
| ES2688547T3 (en) | Coating bath for non-electrolytic deposition of nickel layers | |
| CN103726056B (en) | The protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal | |
| Zhang et al. | Electroless deposition of Ni–W–P coating on AZ91D magnesium alloy | |
| CN102892924B (en) | Beta-amino acid comprising electrolyte and method for the deposition of a metal layer | |
| CN102817056B (en) | Electroplating process for lead wire frame palladium-nickel alloy plating layer | |
| TW460613B (en) | Tin alloy plating compositions | |
| CN102162095A (en) | Anti-discoloring protective agent for silver plating and preparation method as well as application method thereof | |
| Faraji et al. | An investigation on electroless Cu–P composite coatings with micro and nano-SiC particles | |
| CN101899688B (en) | Cyanide-free gold plating solution for plating gold | |
| CN102492968A (en) | Copper plating method on brass base material | |
| CN101838828A (en) | Cyanogen-less gold plating solution | |
| Faraji et al. | Corrosion resistance of electroless Cu–P and Cu–P–SiC composite coatings in 3.5% NaCl | |
| JP2012052222A (en) | Composition of nanoparticles | |
| Hosseini et al. | Deposition and corrosion resistance of electroless Ni-PCTFE-P nanocomposite coatings | |
| CN100595006C (en) | Method for preparing copper cladded iron composite powder | |
| CN102061495B (en) | Graphite dispersant agent in cyanide-free electrodeposition silver-graphite alloy plating solution and preparation method | |
| Faraji et al. | Effect of SiC on the corrosion resistance of electroless Cu–P–SiC composite coating | |
| CN104120465B (en) | A kind of Electroplate liquid of alkaline zinc-nickel alloy and its preparation method and application | |
| CA1222720A (en) | Zinc cobalt alloy plating | |
| CN111519219A (en) | Silver electroplating liquid composite additive and preparation method and application thereof | |
| Ding et al. | The electrodeposition of low-Sn imitation gold Cu–Sn alloy from EDTA-tartrate double complexing agents | |
| CN108495952A (en) | As the water solubility of electroless metal deposition stabilizer and the phospha-adamantane of air-stable | |
| CN112501615B (en) | Deplating solution for electroplated layer of external lead of integrated circuit and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170324 Address after: 528441 Guangdong City, the people of the town of sand Aberdeen Industrial Park Ping Road (Hai Rong company, building two, floor, second) Patentee after: Zhongshan Rui Rui metal plating technology consulting Co., Ltd. Patentee after: Hubei Engineering University Address before: 528441 Zhongshan City, the people of the town of sand Aberdeen Industrial Park Ping Road Patentee before: Zhang Wenbo Patentee before: Hubei Engineering University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191127 Address after: 523133 Room 101, building 62, No.126, guangma Avenue, Machong Town, Dongguan City, Guangdong Province Co-patentee after: Hubei Engineering University Patentee after: Dongguan Yichuang Surface Treatment Technology Co., Ltd Address before: 528441 Guangdong City, the people of the town of sand Aberdeen Industrial Park Ping Road (Hai Rong company, building two, floor, second) Co-patentee before: Hubei Engineering University Patentee before: Zhongshan Rui Rui metal plating technology consulting Co., Ltd. |
|
| TR01 | Transfer of patent right |