CN106544676A - Modified volatile rust prevention fibre board of a kind of Graphene and preparation method thereof - Google Patents
Modified volatile rust prevention fibre board of a kind of Graphene and preparation method thereof Download PDFInfo
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- CN106544676A CN106544676A CN201710011564.9A CN201710011564A CN106544676A CN 106544676 A CN106544676 A CN 106544676A CN 201710011564 A CN201710011564 A CN 201710011564A CN 106544676 A CN106544676 A CN 106544676A
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- graphene
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- volatile rust
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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
- C23F11/02—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in air or gases by adding vapour phase inhibitors
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Modified volatile rust prevention fibre board of a kind of Graphene and preparation method thereof.By compound recipe vapour phase inhibitor by BTA, triethanolamine, sodium benzoate in mass ratio be 1.2～2.1：1.4～2.5：0.9～1.5 ratio is added in the graphene oxide aqueous dispersions that mass concentration is 0.5mg/mL, is stirred；It is configured to the vapour phase inhibitor aqueous dispersions that mass concentration is 5%-70%；Vapour phase inhibitor aqueous solution is coated in using coating machine for two surfaces of paper fiber, air drying obtains load capacity and is about 10-80g/m2Volatile rust prevention fibre board.The modified volatile rust prevention fibre board of the Graphene can designed size and thickness, be easy to remove after use, in compounding vapour phase inhibitor, do not contain the harmful constituents such as nitrite, it is easy to use efficiently, Environmental Safety.
Description
Technical field：
The present invention relates to a kind of modified volatile rust preventive material of Graphene and packing articles field, in particular to a kind of Graphene
Modified volatile rust prevention fibre board and preparation method thereof.
Background technology：
In the today in modern industrialization epoch, metal and its product are seen everywhere.But due to the oxygen being widely present in air
The salt contained in gas and water steam, sour gas and vapor, it is easy to which atmospheric corrosion occurs, generates in metal surface and aoxidizes
Thing and hydroxide mixture, so as to damaging their performance and reducing its life-span, can cause a serious accident when serious or cause
Equipment scrapping.During especially metal and its product at sea transport the overland transport moist with hyperpyrexia, it is more prone to meet with corruption
Lose and corrosion occurs.According to statistics, the whole world is every year because the economic loss that corrosion is caused accounts for 3% of GDP then or so, and about 1/3
Steel because corrosion cause loss.Therefore, various metal erosion means of defences cause the concern of people.Conventional at present smears anti-
Rust oils and fatss are owned by France in contact antirust, and not only technique is loaded down with trivial details, take bothersome, effect on driving birds is not good, and also needs to carry out before unpacking
Cleaning by degreasing operation, easily causes the secondary pollution of environment, and antirust oil is not reached for those turning, gap portion
Position, then can not form effective corrosion protection, and this method increasingly can not be received by people.Using vacuum-packing method then into
This is higher, and the extremely difficult reality for large-scale workpiece.Although desiccant antirust cost is relatively low, easy to use, effectively
Time is shorter and affected by environment larger, effect it is difficult to ensure that.
Vapour phase inhibitor (abbreviation of VCI, Volatile Corrosion Inhibitor) is the special synthesis techniques of Jing, answers
With a kind of corrosion inhibitor being prepared from.It individually or can depend on suitable carrier, at normal temperatures and pressures direct gasification.
Cause, in any spatial gaps in operation unit, can all fill and contain by itself adjustable persistently volatilization in sealed environment
There are the mixed gas of the VCI antirust factors, this gas can adsorb when meeting with metal surface thereon, form only one of which or several points
Sub thick fine and close protection film layer.The protection film layer can effectively completely cut off moisture, oxygen and other hazardous atmospheres and metal surface is connect
Tactile property corrosion, suppresses the electrochemical reaction of metal erosion, so as to reach optimal anti-corrosion effect.With traditional rust-proofing method phase
Than VCI materials have many unrivaled advantages.Such as after the completion of metal material is packed or sprayed, vapor phase corrosion inhibitor agent molecule
Just start diverging, vapor phase corrosion inhibitor agent molecule may penetrate into the corner space that traditional antirust oil cannot be covered, and antirust is without dead angle；Gas phase
Inhibition molecule effective ingredient retention time is long, and can extend protective period limit；There are moisture or outside air very moist in metal surface
Under conditions of, corrosion inhibiter also can form protecting film in metal surface and prevent rust corrosion.The volatile rust prevention product master for commonly using at present
Volatile rust preventive oil to be had, volatile rust prevention powder, volatile rust preventive paper and gas-phase antirusting film.Volatile rust preventive oil is added by base oil and auxiliary
Plus agent composition, during use need smear, remove overcoat when it is time-consuming, take a lot of work, it is both unhygienic and dangerous.Volatile rust prevention powder is then needed
Use is packed, antirusting powder is scattered and causes damage after bag breakage.Volatile rust preventive paper toughness is bad, easy breakage, and
The easy moisture absorption in surface, oil suction, cause to pack effect decline, affect antirust function.Although gas-phase antirusting film have it is transparent, flexible,
Can machine-shaping, the features such as barrier is high, but containing the strong carcinogen nitrous acid for disabling in the world in vapour phase inhibitor component
Vapour phase inhibitor is added directly into into blown film in resin, vapour phase inhibitor in salt, and technique disclosed in CN01127534.0
Grain skewness, gained membrane product occur rough surface and crystallization phenomenon；And will be coated with after corrosion inhibiter and bonding agent mixing
Method on plastic sheeting, then energy consumption is big and complex procedures, can not clean manufacturing, easily affects to prevent because mixing uneven
Rust effect.
It can thus be seen that develop one kind all has excellent rust-proof effect to various many metals, and with environment friend
Good, volatile rust preventive material easy to operate, to solving the problems, such as that the corrosion of metal for being related to national economy seems particularly urgent.Papery is fine
Dimension plate is that a kind of wide material sources, degradable inexpensive carrier material, and this material do not allow cracky, and size and dimension can be with
Arbitrarily adjust, with very high water absorbing properties, have higher load capacity to volatile rust prevention liquid, it is ensured that prolonged gas phase
Rust-proof effect.The gas-phase rustproof packaging material based on paper fiber is yet there are no, especially be yet there are no modified based on Graphene
The report of the volatile rust prevention papery fibre board packaging material of composite corrosion inhibitor and preparation method thereof.
The content of the invention：
It is an object of the invention to solve deficiency of the prior art, there is provided a kind of modified volatile rust prevention fibre board of Graphene
And preparation method thereof.
For achieving the above object, the modified volatile rust prevention fibre board of a kind of Graphene that the present invention is provided, it is characterised in that it
Including paper fiber basal layer and gas phase antirust coat, wherein volatile rust prevention layer is applied by coating machine, and compound recipe gas phase is delayed
Erosion agent aqueous dispersions adsorb in paper fiber plate surface, need not add any binding agent；The modified volatile rust prevention of the Graphene is fine
The preparation method of dimension plate, it is characterised in that including step in detail below：Compound recipe vapour phase inhibitor is dissolved in into Graphene aqueous dispersions
In, it is 8.0-9.0 or so to adjust pH value with ammonia, is configured to certain density compound recipe vapour phase inhibitor aqueous dispersions；Using painting
Compound recipe vapour phase inhibitor aqueous solution is coated in cloth machine two surfaces of paper fiber, and air drying obtains Graphene and changes
Property volatile rust prevention fibre board.
Preferably, the paper fiber is the degradation material that thickness is about 3-15mm；Volatile rust prevention layer is fine in papery
Load capacity on dimension plate is about 10-80g/m2。
Preferably, the preparation method of the modified volatile rust prevention fibre board of described a kind of Graphene, it is characterised in that described multiple
Square vapour phase inhibitor is made up of BTA, triethanolamine, sodium benzoate, and their mass ratio is 1.2～2.1：1.4～
2.5：0.9～1.5；First BTA and triethanolamine are added by above-mentioned mass ratio when preparing vapour phase inhibitor aqueous dispersions
To in Graphene aqueous dispersions of the mass concentration for 0.5mg/mL, it is proportionally added into sodium benzoate after being sufficiently stirred for again, fully stirs
Mix uniform；The mass concentration of the vapour phase inhibitor aqueous dispersions of preparation is 5%-70%.
Preferably, the Graphene is graphene oxide；What described Graphene aqueous dispersions were prepared by ultrasound；
After the compound recipe vapour phase inhibitor is added in Graphene aqueous dispersions, the vapour phase inhibitor of alkalescence can be with graphene oxide edge
Carboxyl, hydroxyl and epoxy radicals interact, be equably supported on graphene nanometer sheet, increase its specific surface area, improve gas
Phase corrosion inhibiting ability, extends the vapor phase corrosion inhibitor time.
Beneficial effects of the present invention are embodied in：There is provided a kind of Graphene modified volatile rust prevention fibre board, first using oxidation
The carboxyl of graphene edge, hydroxyl and cycloalkyl groups, are interacted with alkaline vapour phase inhibitor, they are carried on Graphene
Surface, increases the specific surface area of volatile rust prevention fibreboard surface volatile rust prevention layer, improves vapor phase corrosion inhibitor ability, extends vapor phase corrosion inhibitor
Time.The vapour phase inhibitor aqueous dispersions for being used are first to be compounded in graphenic surface by compound recipe corrosion inhibiter full and uniform, and Jing is applied
The specific surface area of volatile rust prevention fibreboard surface volatile rust prevention layer can be increased after applying, and the high-hydroscopicity paper fiber for adopting can
Improve compounding vapour phase inhibitor load capacity；Volatile rust prevention fibre board can designed size and thickness as requested, be easy to after use
Remove, in compounding vapour phase inhibitor, do not contain the harmful constituents such as nitrite, use easier, efficient, environmentally friendly and peace
Entirely.
Specific embodiment：
To further understand the present invention, with reference to embodiment, the invention will be further described, but not with any side
Formula limits the present invention.
The preparation method that the modified volatile rust prevention fibre board of Graphene in following embodiments is adopted includes step in detail below：
Embodiment 1：
It is first 1.5 in mass ratio by corrosion inhibiter BTA and triethanolamine：2.0 ratio is added to mass concentration
In the Graphene aqueous dispersions of 0.5mg/mL, again by triethanolamine after being sufficiently stirred for：Sodium benzoate mass ratio is 2.0：1.2 ratio
Example adds sodium benzoate, and it is 8.0-9.0 or so to adjust pH value with ammonia, is stirred, vapour phase inhibitor aqueous dispersions
Mass concentration is 25%, adopts coating machine that vapour phase inhibitor aqueous solution is coated in thickness for two of paper fiber of 6mm
Surface, air drying obtain load capacity and are about 20g/m2Volatile rust prevention fibre board a.
Embodiment 2：
It is first 2.0 in mass ratio by corrosion inhibiter BTA and triethanolamine：1.5 ratio is added to mass concentration
In the Graphene aqueous dispersions of 0.5mg/mL, again by triethanolamine after being sufficiently stirred for：Sodium benzoate mass ratio is 1.5：1.2 ratio
Example adds sodium benzoate, and it is 8.0-9.0 or so to adjust pH value with ammonia, is stirred, vapour phase inhibitor aqueous dispersions
Mass concentration is 25%, adopts coating machine that vapour phase inhibitor aqueous solution is coated in thickness for two of paper fiber of 6mm
Surface, air drying obtain load capacity and are about 35g/m2Volatile rust prevention fibre board b.
Embodiment 3：
It is first 1.5 in mass ratio by corrosion inhibiter BTA and triethanolamine：2.5 ratio is added to mass concentration
In the Graphene aqueous dispersions of 0.5mg/mL, again by triethanolamine after being sufficiently stirred for：Sodium benzoate mass ratio is 2.5：1.0 ratio
Example adds sodium benzoate, and it is 8.0-9.0 or so to adjust pH value with ammonia, is stirred, vapour phase inhibitor aqueous dispersions
Mass concentration is 45%, adopts coating machine that vapour phase inhibitor aqueous solution is coated in thickness for two of paper fiber of 6mm
Surface, air drying obtain load capacity and are about 35g/m2Volatile rust prevention fibre board c.
Embodiment 4：
It is first 1.8 in mass ratio by corrosion inhibiter BTA and triethanolamine：2.1 ratio is added to mass concentration
In the Graphene aqueous dispersions of 0.5mg/mL, again by triethanolamine after being sufficiently stirred for：Sodium benzoate mass ratio is 2.1：1.3 ratio
Example adds sodium benzoate, and it is 8.0-9.0 or so to adjust pH value with ammonia, is stirred, vapour phase inhibitor aqueous dispersions
Mass concentration is 55%, adopts coating machine that vapour phase inhibitor aqueous solution is coated in thickness for two of paper fiber of 6mm
Surface, air drying obtain load capacity and are about 35g/m2Volatile rust prevention fibre board d.
Comparative example 1：
It is 1.5 in mass ratio by corrosion inhibiter BTA, triethanolamine, sodium benzoate：2.5：1.0 ratio is added and is gone
In ionized water, it is 8.0-9.0 or so to adjust pH value with ammonia, is stirred, and the quality of vapour phase inhibitor aqueous dispersions is dense
Spend for 45%, adopt coating machine by vapour phase inhibitor aqueous solution be coated in thickness for 6mm paper fiber two surfaces, it is empty
It is dried in gas, obtains load capacity and be about 35g/m2Volatile rust prevention fibre board b1.
Comparative example 2：
It is first 1.5 in mass ratio by corrosion inhibiter BTA, triethanolamine, sodium benzoate：2.5：1.0 ratio is added
In deionized water, in stating dispersion liquid then up, Graphene is added, the mass concentration for making Graphene is 0.5mg/mL, is adjusted with ammonia
Section pH value is 8.0-9.0 or so, is stirred, and the mass concentration of vapour phase inhibitor aqueous dispersions is 45%, using coating
Vapour phase inhibitor aqueous solution is coated in machine two surfaces of the paper fiber that thickness is 6mm, and air drying is loaded
Amount is about 35g/m2Volatile rust prevention fibre board b2.
5 application effect test example of embodiment
The measure of corrosion inhibition rate, concrete grammar are carried out to volatile rust prevention fibre board prepared by embodiment 1-4 and comparative example 1-2
For：The 45# carbon steel coupons of 30nm × 30nm × 3nm are polished smooth step by step with the sand paper of 180#～240#, deionized water cleaning
Totally, with drying after cotton ball soaked in alcohol defat.To be polished with volatile rust prevention fibre board prepared by embodiment 1-4 and comparative example 1-2
Good 45# carbon steels test piece sandwiches, then the test piece decussation sandwiched with nylon rope binds, be positioned over temperature for (49 ±
1) DEG C, in the climatic chamber of relative temperature about 95.Its corrosion degree is observed after 40 days and oxidation rate and corrosion inhibition rate is calculated：
η=100 × (Δ m0- Δ m1)/Δm0, in formula η be corrosion inhibition rate (%), Δ m0For blank assay medium carbon steel test piece
Mass loss (g), Δ m1To sandwich the mass loss (g) of volatile rust prevention fibre board medium carbon steel test piece.The results are shown in Table 1.
Prepare to embodiment 1-4, the volatile rust prevention fibre board of comparative example 1-2 preparation and by certain external vapor phase corrosion inhibitor liquid
Volatile rust prevention fibre board carries out many metal vapor phase rust-proofing performance tests, and test standard is with reference to GB/T 19532-2004, result of the test
It is shown in Table 1.
Table 1 is volatile rust prevention result of the test
Selected from external volatile rust prevention liquid like product market price higher than compound recipe vapour phase inhibitor of the present invention two in table 1
To three times.Comparative test result shows that volatile rust prevention fibre board of the present invention is better than to the rust-proof effect of various metals
The selected volatile rust prevention fibre board prepared by external volatile rust prevention liquid, and volatile rust prevention effect is far superior to comparative example 1-2
The volatile rust prevention fibre board of gained, the wherein best results of embodiment 2 and 4, are the preferred embodiment of the present invention.And implement
The product gas phase rust-proof effect of example 1-4 is substantially better than the sample of comparative example 1-2, shows the functional group of graphene oxide and big
Specific surface area vapour phase inhibitor is evenly dispersed in into nanometer sheet surface, increase its volatility, improve vapor phase corrosion inhibitor performance.
Volatile rust prevention fibre board price of the present invention only has 1/2nd or 1/3rd of same kind of products at abroad, and nontoxic secondary work
With, it is free from environmental pollution, meet national environmental standard requirement, imported product can be replaced completely.Think that their gas phase is delayed
Losing mechanism may be：The corrosion inhibiter of volatile rust prevention fibreboard surface evaporate into metal surface, wherein BTA, three ethanol
Amine, sodium benzoate are attached to metal surface, and the N and O atom in inhibitor molecular contains lone pair electrons, can be with the d electronics of Fe
Unoccupied orbital forms coordinate bond, there occurs chemisorbed, makes compound corrosion inhibitor form firm adsorbed film in metal surface, to suppress
The contact of oxygen and water to metal surface；Additionally, due to adsorption of the fibre board to corrosion inhibiter so that corrosion inhibiter slowly discharges
Out, good rust-proof effect had not only been played but also its antirust time can have been extended.
Take volatile rust prevention fibre board prepared by equivalent embodiment 2 and 4, comparative example 1-2 and by certain external vapor phase corrosion inhibitor liquid
The volatile rust prevention fibre board of preparation is respectively placed in the saline solution of neutral 0.5mol/L of equivalent, and solution is determined after certain hour
The concentration of middle BTA, is as a result listed in table 2.Result from table is it can clearly be seen that the addition of Graphene is slow to gas phase
Erosion agent has certain adsorption, with not plus Graphene and physical mixed method add the sample of Graphene to compare, institute of the present invention
The volatile rust prevention fibre board stated has obvious advantage in terms of gas-phase slow-release antirust, can play the work of control release and slow release
With.
Table 2 is vapor phase corrosion inhibitor result
Claims (4)
1. the modified volatile rust prevention fibre board of a kind of Graphene, it is characterised in that it includes paper fiber basal layer and volatile rust prevention
Layer, wherein volatile rust prevention layer are applied by coating machine, and compound recipe vapour phase inhibitor aqueous dispersions are adsorbed in paper fiber table
Face, need not add any binding agent；The preparation method of the modified volatile rust prevention fibre board of described Graphene, it is characterised in that include
Step in detail below：Compound recipe vapour phase inhibitor is dissolved in Graphene aqueous dispersions, it is 8.0-9.0 left to adjust pH value with ammonia
The right side, is configured to certain density compound recipe vapour phase inhibitor aqueous dispersions；Compound recipe vapour phase inhibitor aqueous solution is applied using coating machine
Apply in two surfaces of paper fiber, air drying, obtain the modified volatile rust prevention fibre board of Graphene.
2. a kind of modified volatile rust prevention fibre board of Graphene according to claim 1, it is characterised in that the paper fiber
Plate is the degradation material that thickness is about 3-15mm；Load capacity of the volatile rust prevention layer on paper fiber is about 10-80g/
m2。
3. a kind of preparation method of the modified volatile rust prevention fibre board of Graphene according to claim 1, it is characterised in that institute
State compound recipe vapour phase inhibitor to be made up of BTA, triethanolamine, sodium benzoate, their mass ratio is 1.2～2.1：1.4
～2.5：0.9～1.5；First BTA and triethanolamine are added by above-mentioned mass ratio when preparing vapour phase inhibitor aqueous dispersions
Enter in the Graphene aqueous dispersions to mass concentration for 0.5mg/mL, after being sufficiently stirred for, be proportionally added into sodium benzoate again, stir
Uniformly；The mass concentration of the vapour phase inhibitor aqueous dispersions of preparation is 5%-70%.
4. a kind of preparation method of the modified volatile rust prevention fibre board of Graphene according to claim 3, it is characterised in that institute
Graphene is stated for graphene oxide；Obtained by described Graphene aqueous dispersions are prepared by ultrasound；The compound recipe vapor phase corrosion inhibitor
After agent is added in Graphene aqueous dispersions, the vapour phase inhibitor of alkalescence can be with the carboxyl at graphene oxide edge, hydroxyl and ring
Epoxide interacts, and is equably supported on graphene nanometer sheet, increases its specific surface area, improves vapor phase corrosion inhibitor ability, extends
The vapor phase corrosion inhibitor time.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710011564.9A CN106544676A (en) | 2017-01-07 | 2017-01-07 | Modified volatile rust prevention fibre board of a kind of Graphene and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710011564.9A CN106544676A (en) | 2017-01-07 | 2017-01-07 | Modified volatile rust prevention fibre board of a kind of Graphene and preparation method thereof |
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| CN106544676A true CN106544676A (en) | 2017-03-29 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019011077A1 (en) * | 2017-07-13 | 2019-01-17 | 山东大业股份有限公司 | Gas phase rust-resistant material used for various metals and preparation method therefor |
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| CN2554113Y (en) * | 2002-05-24 | 2003-06-04 | 金荣范 | Compound packing plate for packing metal material |
| CN103088717A (en) * | 2012-10-15 | 2013-05-08 | 布兰诺工业包装材料(上海)有限公司 | Laminated gas-phase rustproof packaging material and manufacturing method thereof |
| CN103210120A (en) * | 2010-10-13 | 2013-07-17 | 国民油井华高有限公司 | Releasable corrosion inhibitors |
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2017
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| CN2554113Y (en) * | 2002-05-24 | 2003-06-04 | 金荣范 | Compound packing plate for packing metal material |
| CN103210120A (en) * | 2010-10-13 | 2013-07-17 | 国民油井华高有限公司 | Releasable corrosion inhibitors |
| CN103088717A (en) * | 2012-10-15 | 2013-05-08 | 布兰诺工业包装材料(上海)有限公司 | Laminated gas-phase rustproof packaging material and manufacturing method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019011077A1 (en) * | 2017-07-13 | 2019-01-17 | 山东大业股份有限公司 | Gas phase rust-resistant material used for various metals and preparation method therefor |
| US11603494B2 (en) * | 2017-07-13 | 2023-03-14 | Shandong Daye Co., Ltd. | Gas phase rust-resisting material for various metals and preparation method thereof |
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