CN109234740A - 7075 aluminium alloy corrosion inhibiter, microemulsified processing stoste and preparation method thereof - Google Patents
7075 aluminium alloy corrosion inhibiter, microemulsified processing stoste and preparation method thereof Download PDFInfo
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- CN109234740A CN109234740A CN201811242456.3A CN201811242456A CN109234740A CN 109234740 A CN109234740 A CN 109234740A CN 201811242456 A CN201811242456 A CN 201811242456A CN 109234740 A CN109234740 A CN 109234740A
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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
- 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
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- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/38—Heterocyclic nitrogen compounds
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- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
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- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
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- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
- C10M2215/224—Imidazoles
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2225/04—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
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- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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Abstract
The invention belongs to metal working fluid technical fields, aim to solve the problem that the problem that phosphorus content is excessively high in the working fluid for being currently used for 7075 aluminium alloys, a kind of 7075 aluminium alloy corrosion inhibiter are disclosed, by volume, including 0.05-0.3 parts contain phosphor corrosion inhibitor and 0.1-1.5 parts of non-phosphate inhibitors；Weight percent containing aliphatic alcohol polyoxyvinethene phosphate in phosphor corrosion inhibitor is greater than or equal to 95%；Non-phosphate inhibitor is water-soluble imidazoline corrosion inhibiter or poly-epoxy succinic acid corrosion inhibiter；The weight percent of imidazoline type cationic compound is greater than or equal to 20% in water-soluble imidazoline corrosion inhibiter, and the weight percent of polyepoxysuccinic acid salt is greater than or equal to 40% in polyepoxysuccinic acid salt corrosion inhibiter.The present invention without the very poor water-soluble imidazoline corrosion inhibiter of corrosion mitigating effect or corrosion mitigating effect or poly-epoxy succinic acid with aliphatic alcohol polyoxyvinethene phosphate by compounding itself to 7075 aluminium alloys, identical even preferably corrosion mitigating effect can be reached using less phosphorus series compound, reduce phosphorus emission.
Description
Technical field
The invention belongs to metal working fluid technical fields, and in particular to the corrosion inhibiter of 7075 aluminium alloys, 7075 aluminium alloys
With microemulsified processing stoste and preparation method thereof.
Background technique
Metal cutting process is to obtain the workpiece for meeting technique requirement, using lathe by metal extra on device
With the process of grinding tool grinding or cutter cutting.In process, the frictional heat generation between grinding tool or cutter and workpiece causes lathe
Localized hyperthermia, this localized hyperthermia will cause the Physical and mechanical properties etc. of metal material to change, and the performance change of material
Process itself is also influenced in turn, is also easy to produce serious tool wear, the reduction of workpiece surface machining accuracy and surface quality
The consequences such as variation.Therefore, during intermetallic composite coating, metal working fluid is usually used, to play cooling and lubrication effect
Fruit.
Since in machining metal material, metal material constantly generates fresh metal surface, these surfaces have compared with
High chemical activity, when touching the corrosion products that cutting fluid is decomposed or oxidation generates, it may occur that electrochemical reaction.It is this
Electrochemical reaction under liquid film can be such that metal material surface is corroded, to workpiece surface loss of gloss, blackening or long hickie occur
Phenomena such as.Therefore, metal working fluid will not only consider effect that is cooling and lubricating, and corrosion mitigating effect is also extremely important.And conduct
The corrosion inhibiter of corrosion inhibition is mainly played in metal working fluid, selection just becomes very crucial.
7075 aluminium alloys are a kind of aluminum alloy materials being widely used at present, and it is high rigidity structure that intensity is high, density is low
The ideal material of component, and meet Current electronic and automobile industry and pursue more frivolous demand.But 7075 aluminium alloys is anticorrosive
Performance is bad, thus in production process using to the corrosion inhibition of working fluid propose more strict requirements.Currently, I
The advanced cutting fluid of water base fully synthetic cutting fluid or import is generallyd use in state's high and advanced industry to the processing of 7075 aluminium alloys, and
This few class cutting fluid mostly uses phosphorus family corrosion inhibitor.Compared to other kinds of corrosion inhibiter, phosphorus family corrosion inhibitor has 7075 aluminium alloys
There is incomparable corrosion mitigating effect.But it is higher that phosphorus content in the processing liquid system of phosphorus family corrosion inhibitor is used alone, and processes stoste
The volume fraction of middle phosphorus-containing compound reaches 1.8%-2.5%, every to use one ton of processing if processing stoste is diluted 20 times of uses
Dilution of stock will be discharged 1 kilogram or so of phosphorus-containing compound, cause water eutrophication, aggravate environmental pressure, not be inconsistent
Close the theory of green economy sustainable development.
Summary of the invention
The first technical problem to be solved by the present invention is: providing 7075 aluminium that a kind of phosphorus content is few and corrosion inhibition is good
Alloy corrosion inhibiter.
Second technical problem of solution of the present invention is: providing a kind of function admirable and few 7075 aluminium of phosphorus content close
Gold processes stoste with microemulsified.
For first technical problem, the technical scheme adopted by the invention is as follows: a kind of 7075 aluminium alloy corrosion inhibiter are pressed
Stereometer, including 0.05-0.3 parts contain phosphor corrosion inhibitor and 0.1-1.5 parts of non-phosphate inhibitors；It is described to contain poly alkyl alcohol in phosphor corrosion inhibitor
The weight percent of ethylene oxide ether phosphate is greater than or equal to 95%；The non-phosphate inhibitor be water-soluble imidazoline corrosion inhibiter or
Poly-epoxy succinic acid corrosion inhibiter；The weight percent of imidazoline type cationic compound is big in the water-soluble imidazoline corrosion inhibiter
In or be equal to 20%, the weight percent of polyepoxysuccinic acid salt is greater than or equal in the polyepoxysuccinic acid salt corrosion inhibiter
40%.
In the technical scheme, by by water solubility very poor without corrosion mitigating effect or corrosion mitigating effect to 7075 aluminium alloys itself
Imidazoline inhibitor or poly-epoxy succinic acid are compounded with aliphatic alcohol polyoxyvinethene phosphate, and 0.05-0.3 parts of fatty alcohols are used only
Polyoxyethylene ether phosphate corrosion inhibiter is with regard to attainable corrosion mitigating effect and 0.3 part of aliphatic alcohol polyoxyvinethene phosphate is used alone
The attainable corrosion mitigating effect of corrosion inhibiter institute is identical, even more preferably (is specifically shown in embodiment).And water-soluble imidazoline is without phosphorus, nothing
The very strong environmental protection agent of poison, biological degradability, and poly-epoxy succinic acid is even more the green chemical of without phosphorus nitrogen-free, the two makes
Synergistic function is played with the corrosion inhibition to fatty alcohol polyoxyethylene ether phosphoric acid, reduces fatty alcohol polyoxyethylene ether phosphorus
The dosage of acid reduces harm of the corrosion inhibiter to environment under the premise of not reducing corrosion inhibition.
Preferably, the molecular formula of the aliphatic alcohol polyoxyvinethene phosphate is R (C2H4O)3OPO3H2, wherein R is C8-10
Alcohol, isooctanol, laruyl alcohol, C12-14 alcohol, ten alcohol of isomery, isomerous tridecanol or C16-18 alcohol；The imidazoline type cationization
Conjunction object is quaternary ammonium salt cationic imidazoline；The molecular formula of the poly-epoxy succinic acid hydrochlorate is HO (C4H2O5M2)nH, wherein n=
2-10, M indicate Na+,H+,K+Or NH4 +.In this preferred embodiment, inventor has selected the most common fatty alcohol polyoxy second in the market
Alkene ether phosphate corrosion inhibiter, quaternary ammonium salt cationic imidazoline and the lesser poly-epoxy succinic acid hydrochlorate of the degree of polymerization are used as compounding
Agent obtain corrosion inhibiter obtained by the present invention more inexpensively can.
Preferably, 7075 aluminium alloys of the invention with corrosion inhibiter by volume, including 0.1-0.3 part containing phosphor corrosion inhibitor and 0.1-
0.8 part of non-phosphate inhibitor.It is compounded by proportion defined by this preferred embodiment, 0.1-0.3 parts of fatty alcohol polyoxy second is used only
Alkene ether phosphate corrosion inhibiter can reach the corrosion mitigating effect that 0.6 part of aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter is used alone
(being specifically shown in embodiment) greatly reduces the dosage of aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter.
Preferentially, 7075 aluminium alloys of the invention with corrosion inhibiter by volume, including 0.1 part contains phosphor corrosion inhibitor and 0.3 part of water
Dissolubility imidazoline inhibitor.In this optimal technical scheme, matched again containing phosphor corrosion inhibitor and water-soluble imidazoline corrosion inhibiter with this
Match, the corrosion mitigating effect of compounding agent can be made to reach most preferably, and the dosage containing phosphor corrosion inhibitor and the dosage of water-soluble imidazoline compared with
It is few.
Preferably, 7075 aluminium alloys of the invention with corrosion inhibiter by volume, including 0.1 part poly- containing phosphor corrosion inhibitor and 0.5 part
Epoxy succinic acid inhibitor.In this optimal technical scheme, delays containing phosphor corrosion inhibitor and poly-epoxy succinic acid and compounding, energy are matched with this
Reach the corrosion mitigating effect of compounding agent most preferably, and the dosage containing phosphor corrosion inhibitor and the dosage of poly-epoxy succinic acid are less.
For second technical problem, the technical scheme adopted by the invention is as follows: 7075 aluminium alloys of one kind are added with microemulsified
Work stoste, by volume, including 7075 aluminium alloy corrosion inhibiter, 5- described in 0.15-1.8 parts of claim 1-5 any one
30 parts of base oils, 1-5 parts of water-soluble extreme-pressure lubricants, 3-15 parts of water soluble anti-rust agents, 2-10 parts of emulsifiers, 0.5-5 parts help table
Face activating agent, 1-5 part surfactant, 0-2 parts of anticorrosion and bactericidal agents, 0-2 parts of defoaming agents and 15-40 parts of water.
In the technical scheme, by base oil, extreme-pressure lubricant, emulsifier, cosurfactant, fungicide, defoaming agent,
Surfactant, above-mentioned 7075 aluminium alloy corrosion inhibiter, water soluble anti-rust agent and deionized water are allocated as microemulsified processing stoste,
It is Water-In-Oil or oil-in-water dispersion that microemulsified, which processes stoste, compared to oil type working fluid, since moisture content is higher,
Therefore there is better cooling effect, cleaning performance and low cigarette；And compared to aqua type working fluid, due to containing a small amount of oil,
Therefore there is better lubricant effect.And compared with the existing 7075 aluminium alloy working fluids used, reaching identical corrosion mitigating effect
Under the premise of, phosphorus content is less, more environmentally-friendly.
Preferably, the base oil selects No. 25 transformer oil, and the water soluble anti-rust agent selects triethanolamine, the cream
Agent selects T702 petroleum sodium sulfonate, and the cosurfactant selects polysorbate60, and the surfactant selects poly alkyl alcohol
Ethylene oxide ether, the anticorrosion and bactericidal agent select DBNPA, and the defoaming agent selects dimethicone, the wet concentration deionized water
Or distilled water.
Preferably, 7075 aluminium alloys of the invention process stoste with microemulsified, and by volume, including 0.2-0.6 parts of rights are wanted
Ask 7075 aluminium alloy corrosion inhibiter, 8-20 parts of base oils described in 1-5 any one, 1-5 parts of water-soluble extreme-pressure lubricants, 3-10
Part water soluble anti-rust agent, 2-8 parts of emulsifiers, 0.5-2 portions of cosurfactants, 1-5 parts of surfactants, 0.1-1 parts of anti-corrosions are killed
Microbial inoculum, 0.1-1 part defoaming agent and 15-30 parts of water.
Preferably, 7075 aluminium alloys of the invention process stoste with microemulsified, and by volume, including 0.4-0.6 parts of rights are wanted
Ask 7075 aluminium alloy corrosion inhibiter, 10 parts of base oils described in 1-5 any one, 2 parts of water-soluble extreme-pressure lubricants, 5 parts it is water-soluble
Property antirust agent, 4 parts of emulsifiers, 1 portion of cosurfactant, 2 parts of surfactants, 0.4 part of anticorrosion and bactericidal agent, 0.2 part of defoaming agent
With 20 parts of deionized waters.In this optimal technical scheme, each component, which carries out compounding by said ratio, can make the profit for processing stoste
Slip, cooling, low cigarette, easy cleaning, rust inhibition, low bubble property and rustless property all reach preferable level.
The present invention also provides the methods for preparing above-mentioned microemulsified processing stoste, include the following steps:
(1) prepare oil mixture: be successively added while stirring into the base oil the water-soluble extreme-pressure lubricant,
Emulsifier, cosurfactant, fungicide, defoaming agent, surfactant and 7075 aluminium alloy corrosion inhibiter, obtain oily mix
Object.
(2) it prepares aqueous mixture: water soluble anti-rust agent is added while stirring into water, obtain aqueous mixture；
(3) it prepares microemulsified processing stoste: the aqueous mixture being added while stirring extremely into the oil mixture
In microemulsified state, the 7075 aluminium alloy microemulsified processing stoste is obtained；
The invention has the benefit that
1, compared with only using phosphorus series compound as the corrosion inhibiter of active material, 7075 aluminium alloy corrosion inhibiter of the invention
By by itself to 7075 aluminium alloys without the very poor water-soluble imidazoline corrosion inhibiter of corrosion mitigating effect or corrosion mitigating effect or polycyclic oxygen amber
Amber acid is compounded with aliphatic alcohol polyoxyvinethene phosphate, can reach identical even preferably slow using less phosphorus series compound
Effect is lost, phosphorus emission is reduced.
2, compared with existing 7075 aluminium alloy working fluid, 7075 aluminium alloys of the invention have excellent lubrication with working fluid
Property, easy cleaning and rust inhibition, contain less phosphorus-containing compound simultaneously, be conducive to environmental protection.
Detailed description of the invention
Fig. 1 is the appearance and metallographic of the 7075 aluminium alloy microemulsifieds processing stoste corrosion mitigating effect experiment of comparative example 1-6
Photographic result；
Fig. 2 is the appearance and metallographic of the 7075 aluminium alloy microemulsifieds processing stoste corrosion mitigating effect experiment of comparative example 7-14
Photographic result；
Fig. 3 is the appearance and gold of the 7075 aluminium alloy microemulsifieds processing stoste corrosion mitigating effect experiment of comparative example 15-20
Phase photographic result；
Fig. 4 is the appearance and gold of the 7075 aluminium alloy microemulsifieds processing stoste corrosion mitigating effect experiment of comparative example 21-26
Phase photographic result；
Fig. 5 is that the appearance of the 7075 aluminium alloy microemulsifieds processing stoste corrosion mitigating effect experiment of embodiment 28-33 and metallographic shine
Piece result；
Fig. 6 is that the appearance of the 7075 aluminium alloy microemulsifieds processing stoste corrosion mitigating effect experiment of embodiment 34-39 and metallographic shine
Piece result；
Fig. 7 is that the appearance of the 7075 aluminium alloy microemulsifieds processing stoste corrosion mitigating effect experiment of embodiment 40-45 and metallographic shine
Piece result；
Fig. 8 is the SEM imaging results of the 7075 aluminium alloy microemulsifieds processing stoste corrosion mitigating effect experiment of embodiment 37-45；
Fig. 9 is that the appearance of the 7075 aluminium alloy microemulsifieds processing stoste corrosion mitigating effect experiment of embodiment 50-58 and metallographic shine
Piece result.
Specific embodiment
Further explaination is done to the present invention combined with specific embodiments below.
Embodiment 1- embodiment 18
Embodiment 1- embodiment 18 provides 18 kind of 7075 aluminium alloy corrosion inhibiter altogether, proportion such as the following table 1:
| Number | Aliphatic alcohol polyoxyvinethene phosphate inhibiter consumption (mL) | Water-soluble imidazoline inhibiter consumption (mL) |
| Embodiment 1 | 0.1 | 0.4 |
| Embodiment 2 | 0.1 | 0.6 |
| Embodiment 3 | 0.1 | 0.8 |
| Embodiment 4 | 0.3 | 0.4 |
| Embodiment 5 | 0.3 | 0.6 |
| Embodiment 6 | 0.3 | 0.8 |
| Embodiment 7 | 0.5 | 0.4 |
| Embodiment 8 | 0.5 | 0.6 |
| Embodiment 9 | 0.5 | 0.8 |
| Embodiment 10 | 0.05 | 0.4 |
| Embodiment 11 | 0.05 | 0.6 |
| Embodiment 12 | 0.05 | 0.8 |
| Embodiment 13 | 0.1 | 0.1 |
| Embodiment 14 | 0.1 | 0.2 |
| Embodiment 15 | 0.1 | 0.3 |
| Embodiment 16 | 0.05 | 0.1 |
| Embodiment 17 | 0.05 | 0.2 |
| Embodiment 18 | 0.05 | 0.3 |
Table 1
Wherein, the source of aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter and water-soluble imidazoline corrosion inhibiter is preferably as follows
Table 2:
| Title | Type | Manufacturer |
| Water-soluble imidazoline corrosion inhibiter | Quaternary ammonium salt cationic type imidazoline | Shandong You Suo Chemical Industry Science Co., Ltd |
| Aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter | AE0-3P | Shandong You Suo Chemical Industry Science Co., Ltd |
Table 2
Wherein, the molecular formula of AEO-3P is R (C2H4P)3PPP3H2, wherein R indicate C8-10 alcohol, isooctanol, laruyl alcohol,
C12-14 alcohol, ten alcohol of isomery, isomerous tridecanol or C16-18 alcohol.
The 7075 aluminium alloys corrosion inhibiter of embodiment 1-18 the preparation method comprises the following steps: side is stirred into water-soluble imidazoline corrosion inhibiter
Side addition aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter is mixed, is stirred continuously until to obtain uniform compound corrosion inhibitor；Alternatively, past
It is slowly added water-soluble imidazoline corrosion inhibiter in aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter, is stirred continuously until to obtain uniform
Compound corrosion inhibitor, i.e., 7075 aluminium alloy corrosion inhibiter of the invention.
Certainly, the processing of 7075 aluminium alloys described in embodiment 1- embodiment 18 corrosion inhibiter can both be prepared as described above scheme modulation
It is sold or is used for uniform compounding agent, it can also be real by the present embodiment embodiment 1- by the above two component of separated packaging
Proportion described in any an example in example 18 is applied to be used in mixed way.These types of mode all belongs to the scope of protection of the present invention.
Embodiment 19- embodiment 27
Embodiment 19- embodiment 27 provides 9 kind of 7075 aluminium alloy corrosion inhibiter altogether, proportion such as the following table 3:
| Number | Aliphatic alcohol polyoxyvinethene phosphate inhibiter consumption (mL) | Poly-epoxy succinic acid inhibiter consumption (mL) |
| Embodiment 19 | 0.3 | 0.3 |
| Embodiment 20 | 0.3 | 0.9 |
| Embodiment 21 | 0.3 | 1.5 |
| Embodiment 22 | 0.1 | 0.1 |
| Embodiment 23 | 0.1 | 0.3 |
| Embodiment 24 | 0.1 | 0.5 |
| Embodiment 25 | 0.05 | 0.1 |
| Embodiment 26 | 0.05 | 0.2 |
| Embodiment 27 | 0.05 | 0.3 |
Table 3
Wherein, aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter and poly-epoxy succinic acid corrosion inhibiter are preferably such as the following table 4:
| Title | Type | Manufacturer |
| Poly-epoxy succinic acid | The more first anti-incrustation corrosion inhibitors of PESA | Shandong You Suo Chemical Industry Science Co., Ltd |
| Aliphatic alcohol polyoxyvinethene phosphate | AEO-3P | Shandong You Suo Chemical Industry Science Co., Ltd |
Table 4
Wherein, the molecular formula of AEO-3P is R (C2H4O)3OPO3H2, wherein R indicate C8-10 alcohol, isooctanol, laruyl alcohol,
C12-14 alcohol, ten alcohol of isomery, isomerous tridecanol or C16-18 alcohol.The molecular formula of poly-epoxy succinic acid hydrochlorate is HO (C4H2O5M2)nH, wherein n=2-10, M indicate Na+, H+, K+ or NH4+。
The 7075 aluminium alloy corrosion inhibiter of embodiment 19-27 the preparation method comprises the following steps: into poly-epoxy succinic acid corrosion inhibiter side
It stirs side and adds aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter, be stirred continuously until to obtain uniform compound corrosion inhibitor；Alternatively,
It is slowly added poly-epoxy succinic acid corrosion inhibiter into aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter, is stirred continuously until to obtain
One compound corrosion inhibitor.
Certainly, the processing of 7075 aluminium alloys described in embodiment 19- embodiment 27 corrosion inhibiter can both be prepared as described above scheme tune
Uniform compounding agent is made as to sell or use, it can also be real by the present embodiment embodiment 19- by the above two component of separated packaging
Proportion described in any an example in example 27 is applied to be used in mixed way.These types of mode all belongs to the scope of protection of the present invention.
Embodiment 28- embodiment 49
Embodiment 28-49 provides 22 kinds altogether with fatty alcohol polyoxyethylene ether corrosion inhibiter and water-soluble imidazoline corrosion inhibiter
Compounding agent processes stoste as the 7075 aluminium alloys microemulsified of corrosion inhibiter, proportion such as the following table 5:
Table 5
Wherein, the source of each component is preferably such as the following table 6:
Table 6
Water is preferably deionized water.
The preparation method of the 7075 aluminium alloy microemulsifieds processing stoste of embodiment 28-49 includes the following steps:
(1) prepare oil mixture: be successively added while stirring into base oil water-soluble extreme-pressure lubricant, emulsifier,
Cosurfactant, fungicide, defoaming agent, surfactant, aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter and water-soluble miaow
Oxazoline corrosion inhibiter obtains oil mixture, wherein the addition of aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter and water-soluble imidazoline
Sequence can be interchanged, and add after the two can also being mixed to prepare to compounding agent；The addition of other components then should be in strict accordance with upper
Sequence is stated, paste is otherwise easily formed, uniform oil mixture can not be made.
(2) it prepares aqueous mixture: water soluble anti-rust agent is added while stirring into water, obtain aqueous mixture.
(3) it prepares microemulsified processing stoste: the aqueous mixture being added while stirring extremely into the oil mixture
In microemulsified state, the 7075 aluminium alloy microemulsified processing stoste is obtained.
Embodiment 50- embodiment 62
Embodiment 50-62 provides 13 kinds altogether with fatty alcohol polyoxyethylene ether corrosion inhibiter and poly-epoxy succinic acid corrosion inhibiter
Compounding agent processes stoste as the 7075 aluminium alloys microemulsified of corrosion inhibiter, proportion such as the following table 7:
Table 7
Wherein, the source of each component is preferably such as the following table 8:
Table 8
Water is preferably deionized water.
The preparation method of the 7075 aluminium alloy microemulsifieds processing stoste of embodiment 50-62 includes the following steps:
(1) prepare oil mixture: be successively added while stirring into base oil water-soluble extreme-pressure lubricant, emulsifier,
Cosurfactant, fungicide, defoaming agent, surfactant, aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter and polycyclic oxygen amber
Amber acid inhibitor obtains oil mixture, wherein aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter and poly-epoxy succinic acid corrosion inhibiter
Addition sequence can be interchanged, added after the two can also being mixed to prepare to compounding agent；The addition of other components then should be stringent
In the order described above, paste is otherwise easily formed, uniform oil mixture can not be made.
(2) it prepares aqueous mixture: water soluble anti-rust agent is added while stirring into water, obtain aqueous mixture.
(3) it prepares microemulsified processing stoste: the aqueous mixture being added while stirring extremely into the oil mixture
In microemulsified state, the 7075 aluminium alloy microemulsified processing stoste is obtained.
Comparative example 1- comparative example 6
Comparative example 1-6 provides 6 kind of 7075 aluminium alloy microemulsified processing stoste, uses in 6 kind of 7075 aluminium alloy
Microemulsified is processed in stoste, does not add corrosion inhibiter or only using aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter as corrosion inhibiter, has
Body such as table 9:
Table 9
Wherein, the configuration technique and above-described embodiment of manufacturer and product type selected by each component and processing stoste
28-62 is identical, and details are not described herein.
Comparative example 7- comparative example 14
Comparative example 7-14 provides 8 kind of 7075 aluminium alloy microemulsified processing stoste, uses in 8 kind of 7075 aluminium alloy
Microemulsified is processed in stoste, does not add corrosion inhibiter or only using water-soluble imidazoline corrosion inhibiter as corrosion inhibiter, specific such as table 10:
Table 10
Wherein, the configuration technique and above-described embodiment of manufacturer and product type selected by each component and processing stoste
28-62 is identical, and details are not described herein.
Comparative example 15- comparative example 26
Comparative example 15-26 provides 13 kind of 7075 aluminium alloy microemulsified processing stoste, in 6 kind of 7075 aluminium alloy
With in microemulsified processing stoste, corrosion inhibiter is not added or only using poly-epoxy succinic acid corrosion inhibiter as corrosion inhibiter, specific such as table 11:
Table 11
Wherein, the configuration technique and above-described embodiment of manufacturer and product type selected by each component and processing stoste
28-62 is identical, and details are not described herein.
7075 aluminium alloys process the experiment test of stoste corrosion mitigating effect with microemulsified:
1, experimental instrument and equipment
Experiment key instrument equipment is shown in Table 12:
Table 12
2, prepared by test piece
The selection of 2.1 test pieces
Specimen size: (50mm × 25mm × 3mm)
Test piece model: 7075 aluminium alloys
7075 used aluminium alloys of experiment are used into desk-top direct-reading spectrometer in metal laboratory before experiment
SPECTOROMAXX carries out AAS test (atomic absorption spectrography (AAS)), 7075 aluminium alloys and 7075 aluminium of standard that comparative experiments uses
The component content of alloy, the whether standard compliant 7075 aluminium alloys requirement of 7075 aluminium alloys used by judgment experiment.
The pre-treatment of 2.2 test pieces
(1) polishing of test piece: metallography laboratory uses double plate automatic grinding and polishing machine, since test piece is relatively thin, uses for 406 winks
Test piece is sticked on crystal ball waste material by dry glue.Promptly crystal ball prevents test piece from throwing away when use, and test piece is waited for that grinding and polishing face level connects
Polished machine turntable is touched, using abrasive disk polishing strip and corner on the left of equipment, the trace that removal strip is corroded
With scratch dirt etc., grinding process selects corase grinding and fine grinding to make roughing process before subsequent test piece polishes, in process of lapping successively
Strip is ground from thick to thin using P180, P600, P1200, P2400, P4000 model sand paper, requires to make when starting is roughly ground
Test piece ground off 2-3mm depth with P180 sand paper to guarantee subsequent test piece test accuracy, in process of lapping, selectes one and side
Parallel direction keeps this direction motionless and is ground until replacing next model sand paper after strip grinding is smooth, ground
When test piece direction need to change into the vertical direction in previous grinding test piece direction, and so on, the method is to guarantee to grind
The tool marks that previous procedure sand paper coarse sand grinding leaves completely remove, until smooth bright slightly some subtle strokes of fine grinding rear surface
Trace carries out last polishing process using polishing disk on the right side of equipment after the completion of fine grinding, first uniformly sprays on polishing disk polishing flannelet
Polishing fluid, and a selected direction parallel with side carry out polishing until making strip that mirror surface be presented.Ensure that test piece is tested
Face without any scratch, hot spot, etc. bad appearance, the test piece after preparation should properly be stored in dry, clean environment until
Before immersion test.Specific operating method is carried out referring to 0218 standard of SH/T.
(2) it the cleaning and preservation of test piece: by sanding and polishing good test piece hair dryer hot blast drying, then with non-dust cloth or takes off
Rouge cotton dips dehydrated alcohol and cleans surface, is put into sample sack and is sealed for use after hot blast drying.Standby time is after test piece polishing
It counts, is not to be exceeded for 24 hours, it otherwise should sanding and polishing again.
3, test piece experimental program
It is tested using liquid phase static state immersion corrosion to test the corrosion mitigating effect of the microemulsified of different embodiments processing stoste.
Dilution of stock is processed with the microemulsified of 200mL beaker configuration 5%, it is (careful to clamp 7075 aluminium alloy thickness of test piece faces with tweezers
Not encounter test piece tested surface, prevent from leaving scratch influence experimental result) it is put into beaker, so that test piece is completely submerged in dilution
In, it is sealed with drawing film, is adjacent to drawing film and beaker sealing part with adhesive tape, prevents dilution from evaporating, be put into thermostatic drying chamber,
55.0 DEG C of temperature of setting, long run test 8h clamps thickness of test piece side with tweezers after test and takes out test piece, dips nothing with absorbent cotton
Water-ethanol cleans test piece, observes strip situation of change.Specific judgment criteria is as shown in table 13.
| Strip materials | Surface state | Rank | Evaluation result |
| Aluminium alloy | Rustless, gloss is for example new | A grades | It is qualified |
| Aluminium alloy | It is slight dimmed | B grades | It is qualified |
| Aluminium alloy | Moderate is dimmed | C grades | |
| Aluminium alloy | It is serious dimmed | D grades |
Table 13
4, method for testing and detecting
The detection of 4.1 metallographic microscopes
Metallographic microscope is as a kind of common surface analysis method, it may be clearly seen that corrosion coupon under different multiplying
Microscopic appearance feature.It, can be with by metallographic microscope in experiment when naked eyes can not tell the etch state of different test pieces
Obtain more accurate judging result.
4.2SEM/EDS- scanning electron microscope
Scanning electron microscope (SEM) passes through the surface topography of secondary electron signal imaging sample.When test piece is in metallography microscope
When cannot obtain more accurate judging result under mirror, it is necessary to further be detected using scanning electron microscope equipment.SEM matches simultaneously
There is X-ray energy spectrometer attachment, can analyze sample micro-area composition when observing microstructure, obtain accurate quantized data.
5, experimental result
(1) it is only surveyed using aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter as the microemulsified of corrosion inhibiter processing dilution of stock
Test result is shown in Fig. 1.
(2) figure only is seen using water-soluble imidazoline corrosion inhibiter as the microemulsified of corrosion inhibiter processing dilution of stock test result
2。
(3) Fig. 3 and figure only are seen using poly-epoxy succinic acid as the microemulsified of corrosion inhibiter processing dilution of stock test result
4。
(4) using the compounding agent of aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter and water-soluble imidazoline corrosion inhibiter as inhibition
The microemulsified processing dilution of stock test result of agent is shown in Fig. 5, Fig. 6 and Fig. 7；Further SEM points wherein are done to embodiment 37-45
Fig. 8 is shown in analysis, imaging.
(5) using the compounding agent of aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter and poly-epoxy succinic acid corrosion inhibiter as inhibition
The microemulsified processing dilution of stock test result of agent is shown in Fig. 9.
6, experiment conclusion
(1) according to Fig. 1 experimental result, the test piece etch state that additive amount is 0 is compared, only with fatty alcohol polyoxyethylene ether phosphorus
Acid esters corrosion inhibiter has good corrosion mitigating effect to 7075 aluminium alloys really as the microemulsified processing dilution of stock of corrosion inhibiter.
(2) it according to Fig. 1 experimental result, observes by the naked eye and judges that surface appearance and metallograph show result judgement, only
When using aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter as corrosion inhibiter, corrosion of aluminium alloy situation is with fatty alcohol polyoxyethylene ether phosphorus
The increase of the additive amount of acid esters corrosion inhibiter AEO-3P and mitigate, aliphatic alcohol polyoxyvinethene phosphate AEO-3P is greater than in additive amount
Equal to 0.6mL, A grades can achieve to 7075 aluminium alloy corrosion mitigating effects, meet national standard.
(3) experimental result according to fig. 2 compares the experimental comparison group of additive amount 0, only using water-soluble imidazoline corrosion inhibiter as
The microemulsified processing dilution of stock of corrosion inhibiter has certain corrosion mitigating effect to 7075 aluminium alloy test pieces.
(4) experimental result according to fig. 2 is only processing stoste using water-soluble imidazoline corrosion inhibiter as the microemulsified of corrosion inhibiter
Under dilution effect, 7075 aluminium alloy test pieces used are tested after submerging corrosion test, and blocky low and deep loss of gloss occurs in surface
Phenomenon and blocky irregular corrosion area.
(5) experimental result according to fig. 2, when water-soluble imidazoline corrosion inhibiter additive amount is less than 0.6mL, extent of corrosion is with addition
Amount increases and weakens, negative correlation.When greater than 0.6mL, extent of corrosion increases with additive amount and is enhanced, and be positively correlated pass
System.When additive amount is 0.6mL, microemulsified processing dilution of stock has preferable corrosion inhibition to 7075 aluminium alloy test pieces,
The extent of corrosion of 7075 aluminium alloy test pieces can reach B grades, and corroded area is minimum.
(6) according to Fig. 3 and Fig. 4 experimental result, the blank control of poly-epoxy succinic acid corrosion inhibiter is not added in comparison, and addition is poly-
There are a large amount of irregular piebalds in strip in the group of epoxy succinic acid inhibitor.
(7) according to Fig. 3 and Fig. 4 experimental result, increase the dosage of poly-epoxy succinic acid corrosion inhibiter to 7075 aluminium alloy test pieces
Corrosion appearance there is no an apparent change of gradient, the additive amount of poly-epoxy succinic acid corrosion inhibiter 0-1.84mL and 11.54mL with
It is preferable with respect to surface state when upper, but additive amount, in 11.54mL or more, inhibiter consumption is excessively high, and the microemulsified configured adds
Cutting fluid appearance requirement has been not achieved in the dilution of work liquid.Within the scope of 0-2.1mL, strip more serious additive amount occurs
General color corrosion, extent of corrosion is continuous C grade near to be fluctuated.
(8) according to Fig. 5, Fig. 6, Fig. 7 and Fig. 8 experimental result, water-soluble imidazoline corrosion inhibiter and fatty alcohol polyoxyethylene ether
The compounding agent of phosphate corrosion inhibiter 7075 aluminium alloys used to experiment in biggish concentration range have preferable inhibition to make
With.When the aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter of 0.05-0.3mL and the water-soluble imidazoline corrosion inhibiter of 0.1-0.8mL
When compounding, the dilution of microemulsified processing stoste can reach A- grades and the above rank to the corrosion mitigating effect of 7075 aluminium alloys, with
It only compares, delays using 0.3mL aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter as the microemulsified of corrosion inhibiter processing dilution of stock
It is quite or more preferable to lose effect.When 0.1-0.3mL aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter and 0.1-0.8mL water solubility imidazoles
When quinoline corrosion inhibiter compounds, the dilution of microemulsified processing stoste can reach A grades or more to the corrosion mitigating effect of 7075 aluminium alloys
Rank, with only using 0.6mL aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter as the microemulsified of corrosion inhibiter process dilution of stock
Corrosion mitigating effect it is suitable or even effect is more preferable, achieved the purpose that reduce aliphatic alcohol polyoxyvinethene phosphate inhibiter consumption.
In conjunction with SEM feature image, (0.1mLAEO-3P, 0.3mL the water solubility miaow of compound proportion selected by embodiment 42 is further determined that
Oxazoline corrosion inhibiter) caused by corrosion mitigating effect it is best.
(9) according to Fig. 9 experimental result, poly-epoxy succinic acid corrosion inhibiter and aliphatic alcohol polyoxyvinethene phosphate inhibition
The compounding agent of agent 7075 aluminium alloys used to experiment in biggish concentration range have preferable corrosion inhibition.Work as 0.05-
When the aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter of 0.3mL is compounded with the poly-epoxy succinic acid corrosion inhibiter of 0.1-1.5mL, micro emulsion
The dilution for changing processing stoste can reach A- grades and the above rank to the corrosion mitigating effect of 7075 aluminium alloys, than only with 0.3mL rouge
Fat alcohol polyoxyethylene ether phosphate corrosion inhibiter will be got well as the corrosion mitigating effect of the microemulsified processing dilution of stock of corrosion inhibiter.When
When the aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter of 0.1-0.3mL is compounded with the poly-epoxy succinic acid corrosion inhibiter of 0.1-1.5mL,
The dilution of microemulsified processing stoste can reach A grades and the above rank to the corrosion mitigating effect of 7075 aluminium alloys, and only with 0.6mL
Aliphatic alcohol polyoxyvinethene phosphate corrosion inhibiter is identical as the corrosion mitigating effect of the microemulsified processing dilution of stock of corrosion inhibiter, very
It is more preferable to effect, achieve the purpose that reduce aliphatic alcohol polyoxyvinethene phosphate inhibiter consumption.In conjunction with SEM feature image
(not shown) determines compound proportion selected by embodiment 55 (0.1mLAEO-3P, 0.5mL poly-epoxy succinic acid corrosion inhibiter) institute
The corrosion mitigating effect of generation is best.
The present invention is not limited to above-mentioned optional embodiment, anyone can show that other are each under the inspiration of the present invention
The product of kind form.Above-mentioned specific embodiment should not be understood the limitation of pairs of protection scope of the present invention, protection of the invention
Range should be subject to be defined in claims, and specification can be used for interpreting the claims.
Claims (10)
1. a kind of 7075 aluminium alloy corrosion inhibiter, it is characterised in that: by volume, including 0.05-0.3 part containing phosphor corrosion inhibitor with
0.1-1.5 parts of non-phosphate inhibitors；The weight percent containing aliphatic alcohol polyoxyvinethene phosphate in phosphor corrosion inhibitor be greater than or
Equal to 95%；The non-phosphate inhibitor is water-soluble imidazoline corrosion inhibiter or poly-epoxy succinic acid corrosion inhibiter；The water solubility miaow
The weight percent of imidazoline type cationic compound is greater than or equal to 20% in oxazoline corrosion inhibiter, the polyepoxysuccinic acid salt
The weight percent of polyepoxysuccinic acid salt is greater than or equal to 40% in corrosion inhibiter.
2. 7075 aluminium alloy corrosion inhibiter according to claim 1, it is characterised in that: the fatty alcohol polyoxyethylene ether phosphorus
The molecular formula of acid esters is R (C2H4O)3OPO3H2, wherein R indicate C8-10 alcohol, isooctanol, laruyl alcohol, C12-14 alcohol, ten alcohol of isomery,
Isomerous tridecanol or C16-18 alcohol；The imidazoline type cationic compound is quaternary ammonium salt cationic imidazoline；The polycyclic
The molecular formula of oxydisuccinic acid hydrochlorate is HO (C4H2O5M2)nH, wherein n=2-10, M indicate Na+,H+,K+Or NH4 +。
3. 7075 aluminium alloy corrosion inhibiter according to claim 1, it is characterised in that: by volume, including 0.1-0.3 parts
It is described to contain phosphor corrosion inhibitor and the 0.1-0.8 parts of non-phosphate inhibitors.
4. 7075 aluminium alloy corrosion inhibiter according to claim 3, it is characterised in that: by volume, including described in 0.1 part
Containing phosphor corrosion inhibitor and 0.3 part of water-soluble imidazoline corrosion inhibiter.
5. 7075 aluminium alloy corrosion inhibiter according to claim 3, it is characterised in that: by volume, including described in 0.1 part
Containing phosphor corrosion inhibitor and 0.5 part of poly-epoxy succinic acid corrosion inhibiter.
6. a kind of 7075 aluminium alloys process stoste with microemulsified, it is characterised in that: by volume, including 0.15-1.8 parts of rights are wanted
Ask 7075 aluminium alloy corrosion inhibiter, 5-30 parts of base oils described in 1-5 any one, 1-5 parts of water-soluble extreme-pressure lubricants, 3-15
Part water soluble anti-rust agent, 2-10 parts of emulsifiers, 0.5-5 portions of cosurfactants, 1-5 parts of surfactants, 0-2 parts of antisepsis and sterilizations
Agent, 0-2 parts of defoaming agents and 15-40 parts of water.
7. aluminium alloy processes stoste with microemulsified according to claim 6, it is characterised in that: the base oil is No. 25 transformations
Device oil, the water soluble anti-rust agent are triethanolamine, and the emulsifier is T702 petroleum sodium sulfonate, and the cosurfactant is
Polysorbate60, the surfactant are fatty alcohol polyoxyethylene ether, and the anticorrosion and bactericidal agent is DBNPA, and the defoaming agent is two
Methyl-silicone oil, the water are deionized water or distilled water.
8. 7075 aluminium alloy according to claim 6 processes stoste with microemulsified, it is characterised in that: by volume, including
7075 aluminium alloy corrosion inhibiter described in 0.2-0.6 parts of claim 1-5 any one, 8-20 parts of base oils, 1-5 parts of water solubilitys
Extreme-pressure lubricant, 3-10 part water soluble anti-rust agent, 2-8 parts of emulsifiers, 0.5-2 portions of cosurfactants, 1-5 parts of surface-actives
Agent, 0.1-1 parts of anticorrosion and bactericidal agents, 0.1-1 parts of defoaming agents and 15-30 parts of water.
9. 7075 aluminium alloy according to claim 6 processes stoste with microemulsified, it is characterised in that: by volume, including
7075 aluminium alloy corrosion inhibiter described in 0.4-0.6 parts of claim 1-5 any one, 10 parts of base oils, 2 parts of water-soluble extreme pressures
Lubricant, 5 parts of water soluble anti-rust agents, 4 parts of emulsifiers, 1 portion of cosurfactant, 2 parts of surfactants, 0.4 part of antisepsis and sterilization
Agent, 0.2 part of defoaming agent and 20 parts of deionized waters.
10. the preparation method that 7075 aluminium alloys described in claim 6-9 any one process stoste with microemulsified, it is characterised in that
Include the following steps:
(1) it prepares oil mixture: the water-soluble extreme-pressure lubricant, emulsification is successively added while stirring into the base oil
Agent, cosurfactant, fungicide, defoaming agent, surfactant and 7075 aluminium alloy corrosion inhibiter, obtain oil mixture；
(2) it prepares aqueous mixture: water soluble anti-rust agent is added while stirring into water, obtain aqueous mixture；
(3) it prepares microemulsified processing stoste: the aqueous mixture is added while stirring into the oil mixture to being in micro-
Emulsified state obtains the 7075 aluminium alloy microemulsified processing stoste；
Wherein, the consumption proportion of each component used in above steps is the same as 7075 aluminium alloys described in right 6-9 any one
With each group distribution ratio in microemulsified processing stoste.
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| CN112376051A (en) * | 2020-09-30 | 2021-02-19 | 苏州豪尔特化工有限公司 | Compound magnesium alloy corrosion inhibitor suitable for corrosion inhibition of nonferrous metals |
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| CN1958848A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Method for restraining corrosion by circulating cooling water of containing sulphur |
| CN102977974A (en) * | 2011-09-02 | 2013-03-20 | 中国石油化工股份有限公司 | Hot rolling lubricating oil composition and use thereof |
| KR101303228B1 (en) * | 2012-10-22 | 2013-09-10 | 성산테크(주) | Equipment-protective compound of a closed heat-system |
| CN104559983A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Corrosion inhibitor composition, corrosion inhibitor, application of corrosion inhibitor and anti-corrosion method of metal component |
| CN108018559A (en) * | 2017-11-30 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of Compositional type corrosion inhibitor for oil field and preparation method thereof |
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Application publication date: 20190118 |