CN108658794A - A kind of green passivator of metal door and window - Google Patents
A kind of green passivator of metal door and window Download PDFInfo
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- CN108658794A CN108658794A CN201810627848.5A CN201810627848A CN108658794A CN 108658794 A CN108658794 A CN 108658794A CN 201810627848 A CN201810627848 A CN 201810627848A CN 108658794 A CN108658794 A CN 108658794A
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- green
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/141—Amines; Quaternary ammonium compounds
- C23F11/142—Hydroxy amines
Abstract
The invention discloses a kind of green passivator of metal door and window, are related to metal door and window processing technology field, contain 2 hydroxyl, 3 butylene, 1 amine hydrochlorate in the green passivator；The passivating solution of the present invention is green safe, and raw material sources are extensive, and passivation rate is fast, efficient, and Chromating Film On Zn Deposits are stablized.
Description
Technical field
The invention belongs to metal door and window processing technology fields, and in particular to a kind of green passivator of metal door and window.
Background technology
Metal door and window is the indispensable part of present building, and metal door and window is corroded in order to prevent, and people generally can
Its surface is handled, chromating processing is now widely used method.Chromating processing is remarkably improved
The resistance to corrosion of aluminium and its alloy surface, while the passivating film has good adhesive force to coating, it is in addition of low cost, thus
Extensive use is arrived, but chromating treatment fluid contains the Cr VI highly unwanted to human body and environment, not only processing procedure
In will produce pollution, and the Cr VI in passivating film will also cause to be handled product and be made to environment when using and discarding in the future
At secondary pollution.
The application of enhancing with people to environmental protection consciousness, Cr VI is gradually severely limited.2 months 2003
13, European Union was issued " waste electronic andelectrical equipment instruction " and " has been harmful to using certain about being limited in electronic electric equipment
Substances Directive ".The former came into force on the 13rd from August in 2004, be to the effect that exported to 10 major class of European Union totally 99 kinds it is electric
Product recycling and processing cost will be born by manufacturer oneself；The latter was then come into force from 1 day July in 2006, was mainly forbidden to Europe
The electronic and electrical equipment of 6 kinds of harmful substances such as leaded, mercury, cadmium, Cr VI, poly- dibromodiphenyl ether and poly- bromo biphenyl is sold by alliance, this
Instruction will be related to 8 major class totally 64 kinds of products.It researches and develops non-toxic or low-toxic substance and is existed with substituting chromating technique gesture
It must go.
Invention content
The purpose of the present invention is for existing problem, provide a kind of green passivator of metal door and window.
The present invention is achieved by the following technical solutions：
A kind of metal door and window green passivator contains 2- hydroxyls -3- butene-1s-amine hydrochlorate in the green passivator.
Further, the 2- hydroxyls -3- butene-1s-amine hydrochlorate preparation method is：
(1) methacrylaldehyde, trimethylsilyl cyanide and three water lithium perchlorates, methacrylaldehyde, trimethyl cyanogen silicon are added successively into reaction kettle
Alkane and three water lithium perchlorate molar ratios are 1:1.8:1.2,80 DEG C are heated to, is stirred 2 hours with 150r/min rotating speeds, is then added again
The ethyl acetate for entering 6 times of methacrylaldehyde quality stirs 20min with 150r/min rotating speeds, is then filtered, obtains filtered fluid, right
Filtered fluid carries out selection evaporation drying, obtains intermediate；
(2) Lithium Aluminium Hydride of 1.5 times of the acetone and its quality of 5 times of its quality is added into intermediate obtained above, is heated to
It 70 DEG C, is stirred 2 hours with 150r/min rotating speeds, then adds the ether of the sodium sulphate and acetone quality 80% of acetone quality 5% again,
40min is stirred with 150r/min rotating speeds, 2 hours is stood, takes supernatant liquor, rotary evaporation boils off ether at room temperature by supernatant liquor
Afterwards, reaction product is obtained, the hydrochloric acid solution that the mass fraction of 2 times of its quality is 12% is added into reaction product, is heated to 55
DEG C, it is stirred 5 hours with 150r/min rotating speeds, obtains reaction solution, the ether of its quality 80% is added into reaction solution, continue to stir
30min then static 2 hours, takes lower aqueous solution, the rare earth chloride of its quality 0.1% is added into lower aqueous solution, stirring
After uniformly, then rotary evaporation drying is carried out to get 2- hydroxyls -3- butene-1s-amine hydrochlorate.
Further, the rare earth chloride is lanthanum chloride.
Further, the green passivator is made of following components by weight：2- hydroxyls -3- butene-1s-amine salt
Hydrochlorate 1.2-1.5, potassium sulfate 5.5-6.5, sodium nitrate 11-13, boric acid 5-8, corrosion inhibiter 3-5, water 90-100.
Further, the water is deionized water.
Further, potassium sulfate and sodium nitrate weight part ratio are 1:2.
Further, the corrosion inhibiter is maltonic acid sodium.
Further, the metal door and window material includes：Iron, aluminium, copper.
Further, the green passivator temperature in use is 40.4-40.6 DEG C.
It is tested by neutral salt spray method：
Aluminum window carries out salt spray test after passivator of the present invention passivation film forming after cleaning and drying.Experimental condition:Temperature (35
DEG C, ± 2) relative humidity>95%, pH value 6.5~7.2, test piece is 15 °~35 ° with vertical plane inclination angle.Experiment 12h terminates to take
Go out test piece, aluminum window surface is unattacked after cleaning does not change colour.
The present invention has the following advantages compared with prior art：The passivating solution of the present invention is green safe, and raw material sources are extensive,
Passivation rate is fast, efficient, Chromating Film On Zn Deposits stablize, the present invention using 2- hydroxyls -3- butene-1s-amine hydrochlorate as chief active at
Point, reasonably combined several substances form complicated composite passivation film on metal door and window surface, when improving conventional passivation
Easily there is the phenomenon that stress cracking in passivating film, effectively enhances the compactness of composite passivation film, effectively enhances its inhibition energy
Power can effectively reduce the micropore between composite passivation film, make film layer more under the action of 2- hydroxyls -3- butene-1s-amine hydrochlorate
Densification enhances the self-healing property and corrosion resistance of composite passivation film.Finally under the mating reaction of each ingredient, passivator tool of the present invention
There is environmental protection, without intense irritation smell, avirulent feature, can significantly reduce the harm to personnel and environment, and effectively drop
Low production cost, the more existing similar product of passivation speed used improve 35% or so, and treated metal door and window corrosion resistant
More preferably, use value is higher for characteristic；It can be seen that by verification experimental verification of the present invention and do not adding 2- hydroxyls -3- butene-1s-amine salt
When hydrochlorate, the passivating film corrosion resistance of generation is greatly lowered, in 2- hydroxyls -3- butene-1s-amine hydrochlorate base passivator with reality
It applies example 1 to differ only in when not adding lanthanum chloride in 2- hydroxyls -3- butene-1s-amine hydrochlorate preparation process, passivating film is corrosion-resistant
Performance reduces by a small margin, it can be seen that, add a certain amount of lanthanum chloride in 2- hydroxyls -3- butene-1s-amine hydrochlorate preparation process
The corrosion resistance of passivating film can be further improved afterwards；Passivation temperature can significantly affect passivating film corrosion resistance, with
The rising of temperature, passivating film corrosion resistance is continuously improved, and when temperature reaches 40.5 DEG C, passivating film corrosion resistance reaches
Most preferably, continue to heat up, passivating film corrosion resistance continuously decreases, and passivation temperature is at 40.4-40.6 DEG C, passivating film corrosion resistance
Best state can be maintained at.
Specific implementation mode
Embodiment 1
A kind of metal door and window green passivator contains 2- hydroxyls -3- butene-1s-amine hydrochlorate in the green passivator.
Further, the 2- hydroxyls -3- butene-1s-amine hydrochlorate preparation method is：
(1) methacrylaldehyde, trimethylsilyl cyanide and three water lithium perchlorates, methacrylaldehyde, trimethyl cyanogen silicon are added successively into reaction kettle
Alkane and three water lithium perchlorate molar ratios are 1:1.8:1.2,80 DEG C are heated to, is stirred 2 hours with 150r/min rotating speeds, is then added again
The ethyl acetate for entering 6 times of methacrylaldehyde quality stirs 20min with 150r/min rotating speeds, is then filtered, obtains filtered fluid, right
Filtered fluid carries out selection evaporation drying, obtains intermediate；
(2) Lithium Aluminium Hydride of 1.5 times of the acetone and its quality of 5 times of its quality is added into intermediate obtained above, is heated to
It 70 DEG C, is stirred 2 hours with 150r/min rotating speeds, then adds the ether of the sodium sulphate and acetone quality 80% of acetone quality 5% again,
40min is stirred with 150r/min rotating speeds, 2 hours is stood, takes supernatant liquor, rotary evaporation boils off ether at room temperature by supernatant liquor
Afterwards, reaction product is obtained, the hydrochloric acid solution that the mass fraction of 2 times of its quality is 12% is added into reaction product, is heated to 55
DEG C, it is stirred 5 hours with 150r/min rotating speeds, obtains reaction solution, the ether of its quality 80% is added into reaction solution, continue to stir
30min then static 2 hours, takes lower aqueous solution, the rare earth chloride of its quality 0.1% is added into lower aqueous solution, stirring
After uniformly, then rotary evaporation drying is carried out to get 2- hydroxyls -3- butene-1s-amine hydrochlorate.
Further, the rare earth chloride is lanthanum chloride.
Further, the green passivator is made of following components by weight：2- hydroxyls -3- butene-1s-amine salt
Hydrochlorate 1.2-1.5, potassium sulfate 5.5-6.5, sodium nitrate 11-13, boric acid 5-8, corrosion inhibiter 3-5, water 90-100.
Further, the water is deionized water.
Further, potassium sulfate and sodium nitrate weight part ratio are 1:2.
Further, the corrosion inhibiter is maltonic acid sodium.
Further, the metal door and window material includes：Iron, aluminium, copper.
Further, the green passivator temperature in use is 40.4-40.6 DEG C.
Embodiment 2
A kind of metal door and window green passivator contains 2- hydroxyls -3- butene-1s-amine hydrochlorate in the green passivator.
Further, the 2- hydroxyls -3- butene-1s-amine hydrochlorate preparation method is：
(1) methacrylaldehyde, trimethylsilyl cyanide and three water lithium perchlorates, methacrylaldehyde, trimethyl cyanogen silicon are added successively into reaction kettle
Alkane and three water lithium perchlorate molar ratios are 1:1.8:1.2,80 DEG C are heated to, is stirred 2 hours with 150r/min rotating speeds, is then added again
The ethyl acetate for entering 6 times of methacrylaldehyde quality stirs 20min with 150r/min rotating speeds, is then filtered, obtains filtered fluid, right
Filtered fluid carries out selection evaporation drying, obtains intermediate；
(2) Lithium Aluminium Hydride of 1.5 times of the acetone and its quality of 5 times of its quality is added into intermediate obtained above, is heated to
It 70 DEG C, is stirred 2 hours with 150r/min rotating speeds, then adds the ether of the sodium sulphate and acetone quality 80% of acetone quality 5% again,
40min is stirred with 150r/min rotating speeds, 2 hours is stood, takes supernatant liquor, rotary evaporation boils off ether at room temperature by supernatant liquor
Afterwards, reaction product is obtained, the hydrochloric acid solution that the mass fraction of 2 times of its quality is 12% is added into reaction product, is heated to 55
DEG C, it is stirred 5 hours with 150r/min rotating speeds, obtains reaction solution, the ether of its quality 80% is added into reaction solution, continue to stir
30min then static 2 hours, takes lower aqueous solution, the rare earth chloride of its quality 0.1% is added into lower aqueous solution, stirring
After uniformly, then rotary evaporation drying is carried out to get 2- hydroxyls -3- butene-1s-amine hydrochlorate.
Further, the rare earth chloride is lanthanum chloride.
Further, the green passivator is made of following components by weight：2- hydroxyls -3- butene-1s-amine salt
Hydrochlorate 1.2-1.5, potassium sulfate 5.5-6.5, sodium nitrate 11-13, boric acid 5-8, corrosion inhibiter 3-5, water 90-100.
Further, the water is deionized water.
Further, potassium sulfate and sodium nitrate weight part ratio are 1:2.
Further, the corrosion inhibiter is maltonic acid sodium.
Further, the metal door and window material includes：Iron, aluminium, copper.
Further, the green passivator temperature in use is 40.4-40.6 DEG C.
Embodiment 3
A kind of metal door and window green passivator contains 2- hydroxyls -3- butene-1s-amine hydrochlorate in the green passivator.
Further, the 2- hydroxyls -3- butene-1s-amine hydrochlorate preparation method is：
(1) methacrylaldehyde, trimethylsilyl cyanide and three water lithium perchlorates, methacrylaldehyde, trimethyl cyanogen silicon are added successively into reaction kettle
Alkane and three water lithium perchlorate molar ratios are 1:1.8:1.2,80 DEG C are heated to, is stirred 2 hours with 150r/min rotating speeds, is then added again
The ethyl acetate for entering 6 times of methacrylaldehyde quality stirs 20min with 150r/min rotating speeds, is then filtered, obtains filtered fluid, right
Filtered fluid carries out selection evaporation drying, obtains intermediate；
(2) Lithium Aluminium Hydride of 1.5 times of the acetone and its quality of 5 times of its quality is added into intermediate obtained above, is heated to
It 70 DEG C, is stirred 2 hours with 150r/min rotating speeds, then adds the ether of the sodium sulphate and acetone quality 80% of acetone quality 5% again,
40min is stirred with 150r/min rotating speeds, 2 hours is stood, takes supernatant liquor, rotary evaporation boils off ether at room temperature by supernatant liquor
Afterwards, reaction product is obtained, the hydrochloric acid solution that the mass fraction of 2 times of its quality is 12% is added into reaction product, is heated to 55
DEG C, it is stirred 5 hours with 150r/min rotating speeds, obtains reaction solution, the ether of its quality 80% is added into reaction solution, continue to stir
30min then static 2 hours, takes lower aqueous solution, the rare earth chloride of its quality 0.1% is added into lower aqueous solution, stirring
After uniformly, then rotary evaporation drying is carried out to get 2- hydroxyls -3- butene-1s-amine hydrochlorate.
Further, the rare earth chloride is lanthanum chloride.
Further, the green passivator is made of following components by weight：2- hydroxyls -3- butene-1s-amine salt
Hydrochlorate 1.2-1.5, potassium sulfate 5.5-6.5, sodium nitrate 11-13, boric acid 5-8, corrosion inhibiter 3-5, water 90-100.
Further, the water is deionized water.
Further, potassium sulfate and sodium nitrate weight part ratio are 1:2.
Further, the corrosion inhibiter is maltonic acid sodium.
Further, the metal door and window material includes：Iron, aluminium, copper.
Further, the green passivator temperature in use is 40.4-40.6 DEG C.
Comparative example 1：It is differed only in embodiment 1 and 2- hydroxyls -3- butene-1s-amine hydrochlorate base passivator is replaced with into Shen
Please number：201410637293.4 matal deactivator.
Comparative example 2：It is differed only in 2- hydroxyls -3- butene-1s-amine hydrochlorate base passivator with embodiment 1 and does not add 2-
Hydroxyl -3- butene-1s-amine hydrochlorate.
Comparative example 3：With embodiment 1 differ only in 2- hydroxyls -3- butene-1s-amine hydrochlorate base passivator with embodiment
1 differs only in 2- hydroxyls -3- butene-1s-amine hydrochlorate preparation process and does not add lanthanum chloride.
Experiment
Sample is commercially available H62 brass, and specification is 30.0mm × 30.0mm × 1.5mm；Embodiment and comparative example method is respectively adopted
Handle sample, every group of 10, sample；
Drip nitric acid method of inspection
Nitric acid is acid with strong oxidizing property, it can directly destroy passivating film, diffuses to Copper substrate by fenestra and fault location, experiment is adopted
It is 55% acid solution Chromating Film On Zn Deposits with mass fraction, QJ standards provide that the time that first bubble is generated when nitric acid drop is more than
6s is qualification；
Table 1
As can be seen from Table 1,2- hydroxyls -3- butene-1s-amine hydrochlorate base passivator generates copper product surface in the present invention
Passivating film excellent corrosion resistance, and when not adding 2- hydroxyls -3- butene-1s-amine hydrochlorate, the passivating film corrosion resistance of generation
It is greatly lowered, differs only in 2- hydroxyl -3- fourths in 2- hydroxyls -3- butene-1s-amine hydrochlorate base passivator with embodiment 1
When not adding lanthanum chloride in alkene -1- amine hydrochlorate preparation process, passivating film corrosion resistance reduces by a small margin, it can be seen that, 2-
Passivating film can be further improved after adding a certain amount of lanthanum chloride in hydroxyl -3- butene-1s-amine hydrochlorate preparation process
Corrosion resistance.
Continue to test, compare influence of the different passivation temperatures to passivating film corrosion resistance, handles and try in 1 method of embodiment
Sample, passivation temperature are variable：
Table 2
As can be seen from Table 2, passivation temperature can significantly affect passivating film corrosion resistance, with the rising of temperature, passivating film
Corrosion resistance is continuously improved, and when temperature reaches 40.5 DEG C, passivating film corrosion resistance reaches best, continues to heat up, passivation
Film corrosion resistance continuously decreases, and for passivation temperature at 40.4-40.6 DEG C, passivating film corrosion resistance can be maintained at best
State.
Claims (9)
1. a kind of green passivator of metal door and window, which is characterized in that contain 2- hydroxyl -3- butylene-in the green passivator
1- amine hydrochlorates.
2. a kind of green passivator of metal door and window according to claim 1, which is characterized in that the 2- hydroxyls -3- fourths
Alkene -1- amine hydrochlorate preparation methods are：
(1) methacrylaldehyde, trimethylsilyl cyanide and three water lithium perchlorates, methacrylaldehyde, trimethyl cyanogen silicon are added successively into reaction kettle
Alkane and three water lithium perchlorate molar ratios are 1:1.8:1.2,80 DEG C are heated to, is stirred 2 hours with 150r/min rotating speeds, is then added again
The ethyl acetate for entering 6 times of methacrylaldehyde quality stirs 20min with 150r/min rotating speeds, is then filtered, obtains filtered fluid, right
Filtered fluid carries out selection evaporation drying, obtains intermediate；
(2) Lithium Aluminium Hydride of 1.5 times of the acetone and its quality of 5 times of its quality is added into intermediate obtained above, is heated to
It 70 DEG C, is stirred 2 hours with 150r/min rotating speeds, then adds the ether of the sodium sulphate and acetone quality 80% of acetone quality 5% again,
40min is stirred with 150r/min rotating speeds, 2 hours is stood, takes supernatant liquor, rotary evaporation boils off ether at room temperature by supernatant liquor
Afterwards, reaction product is obtained, the hydrochloric acid solution that the mass fraction of 2 times of its quality is 12% is added into reaction product, is heated to 55
DEG C, it is stirred 5 hours with 150r/min rotating speeds, obtains reaction solution, the ether of its quality 80% is added into reaction solution, continue to stir
30min then static 2 hours, takes lower aqueous solution, the rare earth chloride of its quality 0.1% is added into lower aqueous solution, stirring
After uniformly, then rotary evaporation drying is carried out to get 2- hydroxyls -3- butene-1s-amine hydrochlorate.
3. a kind of green passivator of metal door and window according to claim 2, which is characterized in that the rare earth chloride is chlorine
Change lanthanum.
4. a kind of green passivator of metal door and window according to claim 1 or 2, which is characterized in that the green passivation
Agent is made of following components by weight：2- hydroxyls -3- butene-1s-amine hydrochlorate 1.2-1.5, potassium sulfate 5.5-6.5, nitric acid
Sodium 11-13, boric acid 5-8, corrosion inhibiter 3-5, water 90-100.
5. a kind of green passivator of metal door and window according to claim 4, which is characterized in that the water is deionization
Water.
6. a kind of green passivator of metal door and window according to claim 4, which is characterized in that potassium sulfate and sodium nitrate weight
It is 1 that amount part, which is compared,:2.
7. a kind of green passivator of metal door and window according to claim 4, which is characterized in that the corrosion inhibiter is the Portugals D-
Grape sodium saccharate.
8. a kind of green passivator of metal door and window according to claim 1, which is characterized in that the metal door and window material
Including：Iron, aluminium, copper.
9. a kind of green passivator of metal door and window according to claim 1, which is characterized in that the green passivator makes
It it is 40.4-40.6 DEG C with temperature.
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| CN201810627848.5A CN108658794A (en) | 2018-06-19 | 2018-06-19 | A kind of green passivator of metal door and window |
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| CN201810627848.5A CN108658794A (en) | 2018-06-19 | 2018-06-19 | A kind of green passivator of metal door and window |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9011572B1 (en) * | 2009-06-02 | 2015-04-21 | University Of Dayton | Method of generating hydrogen from the reaction of stabilized aluminum nanoparticles with water and method of forming stabilized aluminum nanoparticles |
| CN105503624A (en) * | 2016-01-21 | 2016-04-20 | 上海应用技术学院 | Preparation method of 2-hydroxyl-3-butene-1-amine |
| CN106756962A (en) * | 2016-12-02 | 2017-05-31 | 机械科学研究总院青岛分院 | A kind of copper alloy surface passivation technology |
-
2018
- 2018-06-19 CN CN201810627848.5A patent/CN108658794A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9011572B1 (en) * | 2009-06-02 | 2015-04-21 | University Of Dayton | Method of generating hydrogen from the reaction of stabilized aluminum nanoparticles with water and method of forming stabilized aluminum nanoparticles |
| CN105503624A (en) * | 2016-01-21 | 2016-04-20 | 上海应用技术学院 | Preparation method of 2-hydroxyl-3-butene-1-amine |
| CN106756962A (en) * | 2016-12-02 | 2017-05-31 | 机械科学研究总院青岛分院 | A kind of copper alloy surface passivation technology |
Non-Patent Citations (2)
| Title |
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| 辛星: "复合型无毒金属钝化剂的研究", 《中国优秀硕士学位论文全文数据库(电子期刊)工程科技I辑》 * |
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