CN114805932A - Preparation and application of green environment-friendly super-hydrophobic clay - Google Patents
Preparation and application of green environment-friendly super-hydrophobic clay Download PDFInfo
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- CN114805932A CN114805932A CN202110067571.7A CN202110067571A CN114805932A CN 114805932 A CN114805932 A CN 114805932A CN 202110067571 A CN202110067571 A CN 202110067571A CN 114805932 A CN114805932 A CN 114805932A
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- 239000004927 clay Substances 0.000 title claims abstract description 31
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000004113 Sepiolite Substances 0.000 claims abstract description 82
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 82
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 82
- 238000000576 coating method Methods 0.000 claims abstract description 36
- 239000011248 coating agent Substances 0.000 claims abstract description 34
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000003607 modifier Substances 0.000 claims abstract description 11
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 7
- 239000003822 epoxy resin Substances 0.000 claims description 12
- 229920000647 polyepoxide Polymers 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 229920005749 polyurethane resin Polymers 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 229920003180 amino resin Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 21
- 238000005260 corrosion Methods 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 11
- 230000007613 environmental effect Effects 0.000 abstract 1
- 229920006334 epoxy coating Polymers 0.000 description 14
- 239000000203 mixture Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002609 medium Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000010962 carbon steel Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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Abstract
The invention relates to an organic resin modified material, in particular to preparation and application of green environment-friendly super-hydrophobic clay. Dissolving a raw material natural sepiolite by a solvent, and then carrying out modification treatment by a surface modifier to obtain hydrophobic clay; wherein the surface modifier is monoalkoxy titanate. The clay powder obtained by the invention has higher contact angle, lower sliding angle and durable super-hydrophobic property. The obtained powder is combined with an organic coating, so that the hydrophobicity, the flexibility and the like of the organic coating can be effectively improved, and the corrosion resistance of the coating is obviously improved. The invention has the advantages of simple preparation process, low cost, environmental protection, strong modification capability to the coating and wide application prospect in the field of corrosion protection.
Description
Technical Field
The invention relates to an organic coating modified material, in particular to preparation and application of green environment-friendly super-hydrophobic clay.
Background
The organic coating is one of the simple, effective and widest-range technologies in all anti-corrosion measures, and can provide a physical barrier between a corrosion medium and a metal substrate, so that the corrosion of the corrosion medium to the metal substrate is effectively blocked. Corrosion mostly starts to occur at the contact interface between the aqueous medium and the material, however, the organic coating is affected by solvent volatilization during the preparation process and mechanical external force during the use process, so that defects exist on the surface of the coating, corrosive medium invades into the coating, and the failure of the coating is caused. Therefore, there is a need to increase the repellency of aqueous media to coatings, and to reduce the contact area and contact time of the coating with corrosive media, to improve the corrosion resistance of the coating.
Disclosure of Invention
Aiming at the defects of poor protective performance and the like caused by weak mechanical properties of the existing hydrophobic coating, the invention mainly aims to provide green super-hydrophobic clay powder and preparation and application thereof.
In order to achieve the purpose of the invention, the technical route of the invention is as follows:
a preparation method of green environment-friendly super-hydrophobic clay comprises dissolving natural sepiolite as raw material with solvent, and modifying with surface modifier to obtain hydrophobic clay; wherein the surface modifier is monoalkoxy titanate; the monoalkoxy titanate can be KR-TTS, TL-411A, Kr-12, KR-38S, etc.
The raw material is dissolved by dissolving natural sepiolite by a solvent; wherein the solvent is absolute ethyl alcohol, and the weight ratio of the natural sepiolite to the absolute ethyl alcohol is 1: 5-1: 20.
The surface modifier is dissolved by tetraethyl orthosilicate and then is used for modifying the raw material; the volume ratio of the monoalkoxy titanate to the tetraethyl orthosilicate is 1:10-10: 10.
The weight ratio of the tetraethyl orthosilicate to the absolute ethyl alcohol is 1: 2-1: 10.
the raw materials are dissolved by a solvent after being dried, and then the raw materials are added with a surface modifier at room temperature for ultrasonic treatment and then are stirred for modification treatment, so that the super-hydrophobic clay is obtained.
The green environment-friendly super-hydrophobic clay obtained by the method is light yellow powder, the modified clay powder has a higher water contact angle (larger than 150 degrees) and a lower sliding angle (smaller than 5 degrees), the powder cannot be soaked after being contacted with water drops, and the powder does not sink for a long time after being contacted with an aqueous solution.
The application of the green environment-friendly super-hydrophobic clay comprises the following steps: the green environment-friendly super-hydrophobic clay is applied to being used as an organic resin additive.
The super-hydrophobic clay and organic resin are mixed on the surface of the base material to form an organic coating which is used as an anticorrosive coating of the base material.
The mass content of the green environment-friendly super-hydrophobic clay in the organic resin is 2-15%; wherein the organic resin is epoxy resin, acrylic resin, polyurethane resin or amino resin.
The environment-friendly super-hydrophobic clay powder has a good application prospect in metal corrosion prevention, is simple to prepare and low in cost, and can remarkably improve the hydrophobicity, toughness and corrosion resistance of an organic coating.
Compared with the prior art, the invention has the following beneficial effects:
the invention utilizes the monoalkoxy titanate to carry out surface treatment on the sepiolite powder to obtain the functional sepiolite with super-hydrophobic property. The sepiolite powder is added into the organic coating, so that the inherent defects of the organic coating can be effectively filled, the flexibility of the coating is remarkably enhanced, the defects of micropores in the coating can be filled, a transmission channel of a corrosive medium is cut off, and the occurrence of a corrosion process is delayed. The sepiolite powder with super-hydrophobic property obtained by the invention can greatly improve the hydrophobicity of the organic coating and prevent water molecules and the like from penetrating through the coating. In addition, after the sepiolite is subjected to surface treatment by titanate, the sepiolite has good interface compatibility with organic resin, and new pores and interface defects cannot be generated. The invention has wide application range, can be compatible with most organic resins, has good adhesive force, hydrophobicity and salt spray resistance after the prepared organic coating is cured into a film, and has simple preparation process, low cost, excellent anticorrosion effect and strong protection capability.
Drawings
Fig. 1 is a scanning electron microscope image of an unmodified sepiolite and a modified sepiolite provided in an embodiment of the present invention, (a) the modified sepiolite, (b) the unmodified sepiolite;
fig. 2 is a transmission electron microscope image of an unmodified sepiolite and a modified sepiolite provided in the embodiment of the present invention, (a) the modified sepiolite, and (b) the unmodified sepiolite;
fig. 3 is an infrared spectrum diagram of an unmodified sepiolite, a modified sepiolite and a titanate provided by an embodiment of the invention, wherein (a) the unmodified sepiolite, (b) the modified sepiolite and (c) the titanate;
FIG. 4 is a chart showing hydrophobicity of unmodified sepiolite and modified sepiolite in comparison with each other, wherein (a) the modified sepiolite and (b) the unmodified sepiolite are provided by the embodiment of the invention
FIG. 5 is a graph comparing the tensile strength of a modified epoxy coating and an unmodified epoxy coating provided by an embodiment of the present invention, (a) the unmodified epoxy coating, (b) the modified epoxy coating;
fig. 6a is a nyquist plot comparing electrochemical impedance of a modified epoxy coating and an unmodified epoxy coating provided by an example of the present invention.
Fig. 6b is a bode plot comparing electrochemical impedance of a modified epoxy coating and an unmodified epoxy coating provided by an embodiment of the present invention.
Detailed Description
The following examples are presented to further illustrate embodiments of the present invention, and it should be understood that the embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the invention.
Unless defined or stated otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention.
The invention uses the sepiolite which has high theoretical specific surface area, porosity and surface activity, has good adsorption performance on organic or inorganic ions and is easy to carry out surface functionalization treatment as the clay, and then uses the titanate to modify the sepiolite to obtain the modified sepiolite which has super-hydrophobic performance, and can obviously improve the hydrophobic performance of the resin coating after being combined with organic resin. Meanwhile, the modified sepiolite still keeps the original whisker structure and can be used as a nano filler to effectively fill micropores of the organic coating, so that the mechanical property of the organic coating is obviously improved, and the protective property of the organic coating is further improved. Further, the composite coating modified by the sepiolite has multiple performances of toughening, hydrophobicity, corrosion resistance and the like, and has a wide application range.
Example 1
1) Preparing modified sepiolite:
weighing 3.2g of sepiolite raw material, placing the sepiolite raw material in a vacuum drying oven, vacuumizing, and drying for 24 hours at 120 ℃;
the natural sepiolite powder is fibrous magnesium-rich silicate clay mineral, the fiber length can reach several microns, and the natural sepiolite powder is rich in reserves in nature, environment-friendly and nontoxic. A large number of silanol groups exist on the outer surface of the sepiolite, and the hydrophobic modification difficulty is low; the special crystal structure in the sepiolite enables the sepiolite to have large specific surface area, high surface activity, strong adsorbability and excellent filling property, and is suitable to be used as a pigment and filler of an organic coating.
Dissolving the sepiolite in 35g of absolute ethyl alcohol solvent, mechanically stirring for 24 hours, and keeping the temperature at (25 +/-2) DEG C;
③ weighing 2mL of titanate (KR-TTS) and dissolving in 5mL of tetraethyl orthosilicate, carrying out ultrasonic treatment for 30min, pouring the solution into the sepiolite which is mechanically stirred in the step, and continuing stirring for 24 h;
and fourthly, taking out the stirred product, grinding, sieving, putting the product into a sealed bag, and then placing the sealed bag into a drying dish for storage (see figures 1, 2 and 3).
2) The application of the modified sepiolite comprises the following steps:
weighing 10g of E44 epoxy resin and 0.3g of the obtained modified sepiolite, heating and stirring the epoxy resin and the modified sepiolite in a water bath kettle at the temperature of 50 ℃ for 24h, then adding 8g of low molecular polyamide and 2g of absolute ethyl alcohol, uniformly stirring the mixture, then putting the mixture into a vacuum drying oven, after bubbles are removed completely, smearing the mixture on the surface of Q235 carbon steel with the model specification of 20 x 40mm, and finally putting the mixture into an oven at the temperature of 60 ℃ for drying for 48 h.
And (3) carrying out performance test on the modified sepiolite and the composite organic coating obtained by the preparation:
1) scanning Electron Micrographs (SEM) of unmodified sepiolite and modified sepiolite:
as can be seen from fig. 1, the most obvious difference between the modified sepiolite (a) and the unmodified sepiolite (b) is that the internal pores of the structure are changed, and the needle-shaped structure of the modified sepiolite is increased due to the change of the shape and the overall aggregation of the modified sepiolite, so the pores are reduced.
2) Transmission Electron Micrographs (TEM) of unmodified sepiolite and modified sepiolite:
as can be seen from fig. 2, the original needle-like structure of the modified sepiolite in the graph a is not significantly changed, but after the modification, the original needle-like structure of the sepiolite begins to become larger, the surface of the sepiolite begins to become rough from the original smooth surface, and aggregation occurs, so that the pores in the internal structure are significantly reduced.
3) Infrared spectrograms (FTIR) of unmodified sepiolite and modified sepiolite:
as can be seen from FIG. 3, the results of the maps of the unmodified sepiolite (a) and the modified sepiolite (b) are almost identical, the only differences being 2925 and 2853cm -1 And the two characteristic peaks are the saturated C-H characteristic peaks of the titanate (C). Therefore, the modified sepiolite is successfully grafted with the titanate surface modifier, the whole surface energy is reduced, and the hydrophobicity is greatly increased.
4) The hydrophobicity of the modified sepiolite is compared with that of the unmodified sepiolite:
from the comparison of the two graphs a and b in fig. 4, the sepiolite powder after hydrophobic treatment has excellent hydrophobicity, the contact angle between water drops and the powder is more than 150 degrees, the standard of super-hydrophobicity is reached, and the unmodified sepiolite is very easy to dissolve in water; pouring the powder into a beaker containing deionized water, and finding that the modified sepiolite powder completely floats on the water surface, while the unmodified sepiolite powder quickly precipitates underwater. After being placed for 1 month at room temperature, the modified sepiolite powder still floats on the water surface and does not sink, so that the modified sepiolite powder can be proved to have super-strong hydrophobicity.
5) The tensile strength of the modified epoxy coating is compared with that of the unmodified epoxy coating:
and fixing the two ends of each sample on a tensile testing machine, slowly applying tensile stress, gradually increasing the tensile stress along with the increase of time until the sample is broken, and recording the tensile stress value and the tensile distance of the sample at the moment.
As shown in the curve (b) in fig. 5, after 10% of modified sepiolite powder is added to the epoxy resin, although the maximum tensile amount of the epoxy resin is slightly reduced, the tensile distance is obviously increased, and the epoxy resin is broken after being 8mm higher than the common epoxy resin (the curve (a) in fig. 5), which indicates that the flexibility of the epoxy resin is obviously improved by the sepiolite, so that the brittleness property of the epoxy resin can be effectively improved, and the epoxy resin can bear the influence of mechanical external force.
6) Electrochemical impedance test of the modified epoxy coating and the unmodified epoxy coating:
NaCl solution with the concentration of 3.5 percent is taken as electrolyte, a saturated calomel electrode is taken as a reference electrode, a carbon rod is taken as a counter electrode, the test amplitude is 20mV, and the test frequency is 10 mV -2 Hz-10 5 Hz, electrochemical impedance testing was performed using a Parstat P4000+ electrochemical workstation (see fig. 6a and 6 b).
After soaking for 7 days, the impedance of the modified epoxy coating can reach 10 6 Ω·cm 2 (FIG. 6(a)) or more, has a certain protection capability. While the unmodified epoxy coating is reduced to 10 4 Ω·cm 2 (FIG. 6(b)), the protection capability is substantially completely lost.
Example 2
The difference from example 1 is that the sepiolite surface treating agent is different, the modified organic resin is different:
1) preparing modified sepiolite:
weighing 4.6g of sepiolite as a raw material, placing the sepiolite in a vacuum drying oven, vacuumizing, and drying at 130 ℃ for 12 hours;
dissolving the sepiolite in 25g of absolute ethyl alcohol solvent, mechanically stirring for 20 hours, and keeping the temperature at (25 +/-2) DEG C;
③ weighing 5mL of titanate (TL-411A) and dissolving in 6mL of tetraethyl orthosilicate, carrying out ultrasonic treatment for 40min, pouring the solution into the sepiolite under mechanical stirring, and continuing stirring for 36 h;
and fourthly, taking out the stirred product, grinding, sieving, putting the product into a sealed bag, and then putting the sealed bag into a drying dish for storage.
2) Preparing a composite organic coating:
weighing 8g of polyurethane resin and 0.4g of the modified sepiolite prepared above, heating and stirring the mixture in a water bath kettle at the temperature of 50 ℃ for 24 hours, then adding 10g of polyurethane resin curing agent and 6mL of absolute ethyl alcohol, uniformly stirring the mixture, then putting the mixture into a vacuum drying oven for vacuum treatment, after bubbles are removed completely, smearing the mixture on the surface of Q235 carbon steel with the model specification of 20 x 40mm, and then putting the mixture into an oven at the temperature of 80 ℃ for 36 hours.
The obtained toughened organic coating prepared by adding the modified sepiolite has the advantages of improved compactness, more uniform thickness and composition, more excellent compatibility with a metal matrix and improved original brittleness of pure epoxy resin; the hydrophobic treatment of the nano particles enables the integral corrosion resistance to be further improved, and the protection of the metal matrix is more excellent.
It should be understood that various changes, substitutions, and combinations can be made by those skilled in the art without departing from the scope of the invention as defined by the appended claims.
Claims (9)
1. A preparation method of green environment-friendly super-hydrophobic clay is characterized by comprising the following steps: dissolving a raw material natural sepiolite by a solvent, and then carrying out modification treatment by a surface modifier to obtain hydrophobic clay; wherein the surface modifier is monoalkoxy titanate.
2. The method for preparing the green environmentally friendly superhydrophobic clay according to claim 1, characterized in that: the raw material is dissolved by dissolving natural sepiolite by a solvent; wherein the solvent is absolute ethyl alcohol, and the weight ratio of the natural sepiolite to the absolute ethyl alcohol is 1: 5-1: 20.
3. The method for preparing the green environmentally friendly superhydrophobic clay according to claim 1, characterized in that: the surface modifier is dissolved by tetraethyl orthosilicate and then is used for modifying the raw material; the volume ratio of the monoalkoxy titanate to the tetraethyl orthosilicate is 1:10-10: 10.
4. The method for preparing green environmentally friendly superhydrophobic clay according to claim 2, characterized in that: the weight ratio of the tetraethyl orthosilicate to the absolute ethyl alcohol is 1: 2-1: 10.
5. the method for preparing green environmentally friendly superhydrophobic clay according to any one of claims 1-4, characterized in that: the raw materials are dissolved by a solvent after being dried, and then the raw materials are added with a surface modifier at room temperature for ultrasonic treatment and then are stirred for modification treatment, so that the super-hydrophobic clay is obtained.
6. An environmentally friendly superhydrophobic clay obtained by the method of claim 1, wherein: the green superhydrophobic clay prepared according to the method of claim 1.
7. The use of the green environmentally friendly superhydrophobic clay according to claim 1, wherein: the use of the green environmentally friendly superhydrophobic clay according to claim 6 as an additive for organic coatings.
8. Use according to claim 7, characterized in that: the super-hydrophobic clay and organic resin are mixed on the surface of the base material to form an organic coating which is used as an anticorrosive coating of the base material.
9. Use according to claim 8, characterized in that: the mass content of the super-hydrophobic clay in the organic resin is 2-15%; wherein the organic resin is epoxy resin, acrylic resin, polyurethane resin or amino resin.
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| CN202110067571.7A CN114805932B (en) | 2021-01-19 | 2021-01-19 | Preparation and application of environment-friendly super-hydrophobic clay |
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