CN116814136B - Preparation method of PAP (poly (p-phenylene ether) activated carbon sphere-based water-based epoxy intumescent fire-retardant coating - Google Patents
Preparation method of PAP (poly (p-phenylene ether) activated carbon sphere-based water-based epoxy intumescent fire-retardant coating Download PDFInfo
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- CN116814136B CN116814136B CN202310735175.6A CN202310735175A CN116814136B CN 116814136 B CN116814136 B CN 116814136B CN 202310735175 A CN202310735175 A CN 202310735175A CN 116814136 B CN116814136 B CN 116814136B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000000576 coating method Methods 0.000 title claims abstract description 59
- 239000011248 coating agent Substances 0.000 title claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000003063 flame retardant Substances 0.000 title claims abstract description 41
- 239000004593 Epoxy Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000004721 Polyphenylene oxide Substances 0.000 title description 2
- 102100034937 Poly(A) RNA polymerase, mitochondrial Human genes 0.000 claims abstract description 91
- 239000002131 composite material Substances 0.000 claims abstract description 37
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000010959 steel Substances 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- ZKHQWZAMYRWXGA-KQYNXXCUSA-J ATP(4-) Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O)[C@@H](O)[C@H]1O ZKHQWZAMYRWXGA-KQYNXXCUSA-J 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- ZKHQWZAMYRWXGA-UHFFFAOYSA-N Adenosine triphosphate Natural products C1=NC=2C(N)=NC=NC=2N1C1OC(COP(O)(=O)OP(O)(=O)OP(O)(O)=O)C(O)C1O ZKHQWZAMYRWXGA-UHFFFAOYSA-N 0.000 claims description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 10
- 239000003822 epoxy resin Substances 0.000 claims description 10
- 239000008103 glucose Substances 0.000 claims description 10
- 229920000647 polyepoxide Polymers 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 7
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 7
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 7
- 230000001680 brushing effect Effects 0.000 claims description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005488 sandblasting Methods 0.000 claims description 4
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 230000009970 fire resistant effect Effects 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229940079864 sodium stannate Drugs 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- BHTBHKFULNTCHQ-UHFFFAOYSA-H zinc;tin(4+);hexahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Sn+4] BHTBHKFULNTCHQ-UHFFFAOYSA-H 0.000 abstract description 44
- 238000002485 combustion reaction Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 14
- 239000000779 smoke Substances 0.000 abstract description 14
- 239000011701 zinc Substances 0.000 abstract description 9
- 229910052725 zinc Inorganic materials 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005336 cracking Methods 0.000 abstract description 5
- 239000011574 phosphorus Substances 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003973 paint Substances 0.000 abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract 1
- 230000001629 suppression Effects 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 9
- 239000000945 filler Substances 0.000 description 7
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- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920001690 polydopamine Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
The invention discloses a preparation method of PAP activated carbon sphere-based water-based epoxy intumescent fire-retardant coating, which comprises the following preparation steps: (1) preparation of a base material; (2) preparation of CS/PAP@ZHS composite flame retardant; (3) Preparing PAP activated carbon sphere-based water-based epoxy intumescent fire-retardant paint; in the invention, CS balls are effectively combined with nitrogen-containing and phosphorus-containing functional groups in PAP, a stable C-N-P network can be formed in the combustion process, the strength and stability of carbon residue can be improved, and zinc and tin in a zinc hydroxystannate structure can promote the crosslinking of cracking molecules and the formation of carbon, so that the heat shielding effect of the carbon residue is improved; in the combustion process, the back temperature of the PAP activated carbon sphere-based water-based epoxy expansion fireproof coating steel sheet shows the lowest value (171.9 ℃), the highest expansion height and expansion rate are 23.1mm and 17.63%, and the best flame retardance and smoke suppression effect are shown.
Description
Technical Field
The invention belongs to the field of preparation of ultrathin water-based epoxy intumescent fire-retardant coatings, and particularly relates to a preparation method of PAP activated carbon sphere-based water-based epoxy intumescent fire-retardant coatings.
Background
The steel structure has excellent bearing capacity and is widely applied to buildings, bridges, tunnels and other applications; however, it is poorly resistant to high temperatures, making it a great potential fire hazard during use; fireproof coatings with intumescent properties are commonly used as a passive fire protection means for the fire protection of steel substrates. However, the residual carbon formed by the traditional expansion type fireproof paint in the combustion process has the defects of low strength, unsatisfactory heat insulation effect and the like, so that the protection of the traditional expansion type fireproof paint on a steel substrate is very limited; therefore, the addition of some fillers with flame retardant properties is particularly important; the flame retardant is continuously developed to the halogen-free nano reinforcing agent.
Carbon Spheres (CS), a typical carbon material, can be obtained from glucose as a raw material by simple hydrothermal synthesis; the method has the advantages of simple synthesis and low cost, and is an important support for expanding the application range of the method; compared with carbon nanotubes and graphene, the CS surface is rich in functional groups, which provides more convenience for the functionalization of the CS surface; moreover, studies have shown that CS can act as a reinforcing agent to improve the flame retardant properties of organic polymers; however, CS tends to produce significant amounts of black smoke when used alone on polymeric substrates; therefore, it is necessary to use CS in combination with other flame retardants to improve the performance of aqueous fire-resistant coatings.
Disclosure of Invention
Zinc Hydroxystannate (ZHS) is used as a high-efficiency nontoxic flame retardant, and the structure of the Zinc Hydroxystannate (ZHS) contains zinc and tin metal compounds, so that the crosslinking of cracking molecules and the formation of carbon can be promoted; meanwhile, under the action of high temperature, the concentration of inflammable substances can be diluted by the water vapor emission in the ZHS structure, and the temperature near the ignition point is reduced, so that the whole chained combustion reaction is delayed; and the existence of Zn and Sn can promote the dehydration of the cracking molecules to carbon; the Carbon Spheres (CS) in the present invention are preferably obtained by simple hydrothermal reaction starting from glucose; then co-depositing Polydopamine (PDA) and Adenosine Triphosphate (ATP) to obtain activated carbon spheres (CS/PAP) containing a C-N-P network structure; then, zinc Hydroxystannate (ZHS) is grown on the surface of CS/PAP in situ to obtain CS/PAP@ZHS composite flame retardant; the gas phase flame retarding mechanism of ZHS and the catalytic carbon crosslinking synergistic effect of the metal compounds in the structure are beneficial to improving the fire resistance of the composite coating.
In order to achieve the above purpose, the technical scheme adopted by the invention for solving the technical problems is as follows.
A preparation method of PAP activated carbon sphere-based water-based epoxy intumescent fire-retardant coating comprises the following steps.
1. And (3) preparing a base material.
Dispersing Melamine (MEL), pentaerythritol (PER) and ammonium polyphosphate (APP) in a proper amount of deionized water according to a specific proportion, and fully mixing under strong stirring; then, a certain amount of aqueous epoxy emulsion and curing agent are added to the above mixed solution, and stirring is continued for 15-20 minutes to obtain an aqueous expanded epoxy resin base.
2. Preparation of CS/PAP@ZHS composite flame retardant.
(1) A certain amount of glucose is completely dissolved in 100mL of deionized water, and then the glucose solution is poured into a hydrothermal reaction kettle and subjected to hydrothermal reaction for 24 hours at 180 ℃; finally, carbon Spheres (CS) were obtained by washing with a mixture of ethanol and deionized water, and centrifuging.
(2) Dispersing prepared CS (circuit switching) in 100mL of deionized water by ultrasonic, and simultaneously adding a certain amount of dopamine hydrochloride and adenosine triphosphate into CS dispersion under the condition of continuous stirring; subsequently, the pH was adjusted to 8.5 with sodium hydroxide solution (1 mol/L), and the reaction was continued at room temperature for 16 hours to obtain PAP-modified CS (CS/PAP).
(3) Continuously ultrasonically dispersing a certain amount of CS/PAP hybrid in 100mL of deionized water, sequentially adding zinc sulfate and sodium stannate into the mixture, and reacting for 4h; the final suspension is centrifuged and washed repeatedly to obtain CS/PAP@ZHS composite flame retardant; the preparation scheme of the CS/PAP@ZHS composite flame retardant is shown in figure 1.
3. Preparation of PAP activated carbon sphere-based water-based epoxy intumescent fire-retardant coating.
Weighing a CS/PAP@ZHS composite flame retardant with a certain mass, mixing with a base material, and mechanically stirring to form a uniform coating system; then brushing the uniformly mixed water-based intumescent fire-retardant coating on the surface of a steel plate with the size of 10 multiplied by 10cm (sand blasting treatment, sa2 level), curing for 7 days at normal temperature after brushing, and baking for 3 days at 40 ℃ to obtain the PAP activated carbon sphere-based water-based epoxy intumescent fire-retardant coating (namely CS/PAP@ZHS-based water-based intumescent fire-retardant coating).
Further, the mass ratio of the epoxy resin to the expansion system in the step 1 is 1:1-1.2.
Further, the mass ratio of the epoxy resin to the curing agent in the step 1 is 1.5:1-2.0:1.
Further, the ratio of polyphosphate, dipentaerythritol and melamine in the step1 is 6-6.5:3-3.5:1-1.5.
Further, the curing agent in the step 1 may be ethylenediamine, diethylenetriamine, triethylenetetramine.
Further, the concentration of glucose in the step 2 (1) is 150-200g/L.
Further, the CS content in the CS dispersion in step 2 (2) is 2-7mg/mL.
Further, in the step 2 (2), the mass ratio of the dopamine hydrochloride to the adenosine triphosphate is 1:2-3.
Further, the base material in the step 3 accounts for 95.0 to 98.0 percent of the total weight of the uniform dispersion system.
Further, the CS/PAP@ZHS composite flame retardant in the step 3 accounts for 2.0-5.0% of the total weight of the uniform dispersion system.
According to the preparation method of the PAP activated carbon sphere-based water-based epoxy intumescent fireproof coating, from the environmental protection concept, the environment-friendly low-toxicity water-based epoxy resin is used as the base material, and the advantages of CS and the high-efficiency flame retardant ZHS are combined, so that the PAP activated carbon sphere-based water-based epoxy intumescent fireproof coating with the functions of gas-phase flame retardance, catalytic char formation and condensed phase obstruction is developed, and the application range of the environment-friendly multifunctional fireproof coating is widened.
In addition, the PAP activated carbon sphere-based water-based epoxy intumescent fireproof coating provided by the invention has the following beneficial effects.
(1) CS balls are effectively combined with nitrogen-containing and phosphorus-containing functional groups in PAP, and a stable C-N-P network can be formed in the combustion process, so that the strength and stability of carbon residue are improved.
(2) Zinc Hydroxystannate (ZHS) can be decomposed at high temperature to generate water vapor, so that the concentration of the combustible gas is diluted, and part of heat in a combustion area is taken away, so that the fireproof performance of the composite coating is improved.
(3) The metals Zn and Sn in ZHS can promote more cracking products to be converted into stable carbon residue at high temperature, thereby improving the heat shielding effect of the carbon residue.
Drawings
FIG. 1 is a schematic diagram of the preparation flow of CS/PAP@ZHS composite flame retardant.
FIG. 2 is an SEM image of various samples, wherein (a, b) CS, (c, d) CS/PAP, (e, f)
CS/PAP@ZHS。
Figure 3 is an XRD spectrum of the different samples.
FIG. 4 is an XPS spectrum of CS/PAP@ZHS hybrids.
FIG. 5 is a SEM spectrum of the cross-section of a different fire-resistant coating, wherein (a) EP, (b) CS/EP, (c) CS/PAP/EP, (d) ZHS/EP and (e) CS/PAP@ZHS/EP.
FIG. 6 is a graph showing the change in temperature of the backside of the steel sheet and the coated coupon.
FIG. 7 is a macroscopic photograph of different samples after expansion at high temperature.
Fig. 8 shows the expansion height and expansion rate of the different samples.
FIG. 9 shows (a) absorbance curves and (b) smoke density ratios for EP, CS/PAP/EP, ZHS/EP and CS/PAP@ZHS/EP samples.
Figure 10 is an XRD spectrum of the carbon layer after combustion of the different coatings.
FIG. 11 is an SEM topography and EDS spectra of the carbon layer remaining after various sample burn tests, wherein EDS-Mapping photographs of (a) EP, (b) CS/EP, (c) CS/PAP/EP, (d) ZHS/EP, (e) CS/PAP@ZHS/EP and (f-i) CS/PAP@ZHS/EP.
Detailed Description
Example 1.
A preparation method of PAP activated carbon sphere-based water-based epoxy intumescent fireproof coating comprises the following steps.
1. And (3) preparing a base material.
10G of Melamine (MEL), 10g of Pentaerythritol (PER) and 20g of ammonium polyphosphate (APP) are dispersed in a proper amount of deionized water according to a specific proportion and are fully mixed under strong stirring; then, 38g of the aqueous epoxy emulsion and 19g of the curing agent were added to the above mixture, and stirring was continued for 15 to 20 minutes to obtain an aqueous expanded epoxy resin base.
2. Preparation of CS/PAP@ZHS composite flame retardant.
(1) 18G of glucose is completely dissolved in 100mL of deionized water, and then the glucose solution is poured into a hydrothermal reaction kettle and subjected to hydrothermal reaction for 24 hours at 180 ℃; finally, carbon Spheres (CS) were obtained by washing with a mixture of ethanol and deionized water, and centrifuging.
(2) Dispersing prepared 0.5g CS in 100mL deionized water by ultrasonic, and simultaneously adding 0.3g dopamine hydrochloride and 0.6g adenosine triphosphate into CS dispersion under the condition of continuous stirring; subsequently, the pH was adjusted to 8.5 with sodium hydroxide solution (1 mol/L), and the reaction was continued at room temperature for 16 hours to obtain PAP-modified CS (CS/PAP)
(3) The CS/PAP hybrid of 0.3g was further dispersed ultrasonically in 100mL of deionized water, then 0.25g of zinc sulfate and 0.22g of sodium stannate were added sequentially to the above mixture, and the reaction was carried out for 4 hours. The final suspension was centrifuged and washed repeatedly to obtain a CS/PAP@ZHS composite flame retardant.
3. Preparation of PAP activated carbon sphere-based water-based epoxy intumescent fire-retardant coating.
3G of CS/PAP@ZHS composite flame retardant is weighed and mixed with the base material, and a uniform coating system is formed through mechanical stirring; then, the uniformly mixed aqueous intumescent coating was brushed on the surface of a steel plate (sand blasting, sa2 grade) with a size of 10×10cm after pretreatment, cured at normal temperature for 7 days after brushing, and baked at 40 ℃ for 3 days to obtain a PAP activated carbon sphere-based aqueous epoxy intumescent coating (namely CS/PAP@ZHS-based aqueous intumescent coating), and the compositions of the different aqueous intumescent coatings are shown in Table 1.
Table 1 composition of different aqueous intumescent fire protection coatings.
Experimental example 1.
The experimental example shows the analysis result of the related experiment of the preparation method of the PAP activated carbon sphere-based water-based epoxy intumescent fireproof coating.
3.0Wt.% of CS, CS/PAP, ZHS and CS/PAP@ZHS hybrids and base materials are uniformly mixed to prepare 3.0wt.% of CS/EP, CS/PAP/EP, ZHS/EP and CS/PAP@ZHS/EP composite coating respectively; then brushing the uniformly dispersed coating system on the surface of the pretreated steel sheet (Sa 2 level of sand blasting), curing for 7 days at normal temperature after brushing, and baking for 3 days at 40 ℃ to obtain a sample coating; in addition, the experiments were run with pure EP coating as a control.
(1) Microscopic morphologies of CS, CS/PAP and CS/PAP@ZHS hybrids were observed by SEM, and the results are shown in FIG. 2; pure CS (fig. 2 (a, b)) exhibits an extremely smooth standard spherical structure, indicating that the CS manufacturing process is reasonable; for the CS/PAP samples (fig. 2 (c, d)), the microstructure and morphology did not change much, but from its enlarged view (fig. 2 (d)), the surface of the CS became less smooth due to the loading of the PAP; in fig. 2 (e, f) it can be seen that CS is uniformly covered by a large number of cubic nanoparticles, reflecting that ZHS is immobilized on the CS surface by chemical bonds; the chemical bond enables ZHS to be uniformly distributed on the CS/PAP surface, thereby effectively avoiding self aggregation of ZHS, improving the structural stability of CS/PAP@ZHS composite filler and providing conditions for fully exerting the multifunctional flame retardant property of the composite filler.
(2) An X-ray diffractometer (XRD) test was used to monitor the crystal structure characteristics of the different nanofillers, the results are shown in figure 3; the pure CS prepared exhibited a broad and weak diffraction peak at 22.3 °, which is consistent with the (002) crystal plane characteristics of amorphous carbon. After PAP is loaded on the CS surface, diffraction peaks are not changed obviously, and only weak amorphous carbon diffraction signals can be observed, so that the loading process does not cause any change of CS crystal structure; for ZHS, a series of sharp diffraction signals with different intensities are shown at 19.8 °, 22.9 °, 32.6 °, 36.5 °, 38.4 °, 40.2 °, 46.8 °, 52.6 °, 58.3 °, 68.4 ° and 73.1 °, which is consistent with the characteristic peaks of conventional cubic phase ZnSn (OH) 6 (JCPDS: 74-1825); for the CS/PAP@ZHS composite flame retardant, only the ZHS diffraction signal can be observed in the diffraction spectrum, which is probably due to the fact that the strong diffraction behavior of the ZHS masks the characteristic band of weaker CS.
(3) The CS/PAP@ZHS composite flame retardant chemical bond information is shown in FIG. 4; as shown in fig. 4 (a), the full spectrum mainly includes characteristic peaks of C, N, O, P, sn and Zn, which primarily reflect successful insertion of ATP and ZHS; in fig. 4 (b), the binding energy of C1s can be resolved into three photoelectron peaks of 284.7eV,285.8eV and 286.9eV, representing C-C/c=c, C-N/N-c=n and C-O, respectively, which binding energy signature signals are mainly from the CS produced and the ATP molecules inserted; the N1s spectrum (fig. 4 (c)) shows three characteristic peaks corresponding to-NH 2 at 398.7eV, N-H at 399.8eV and =n at 401.1eV, which are generated by the nitrogen-containing group in the ATP structure and PDA; as shown in fig. 4 (d), the O1s spectra can be fitted to four photoelectron signals at 530.5eV,531.5eV,532.4eV and 533.6eV, corresponding to O-Zn/-OH, c=o, P-O and C-O, respectively; for the P2P spectra in FIG. 4 (e), the fitted photoelectron signals for PO 3 -,(PO4)3- and Zn3s appear at 133.5eV,134.6eV and 140.1eV, with PO 3 -and (PO 4)3-) derived primarily from the phosphorus-containing groups in the ATP, and in the Sn3d (FIG. 4 (f)) and Zn2P (FIG. 4 (g)) spectra, the fitted signals for Sn3d5/2 and Sn3d3/2 are at 487.1eV and 495.5eV, while the fitted peaks for Zn2P3/2 and Zn2P1/2 are at 1022.2eV and 1042.3eV, which means successful preparation of ZHS.
(4) FIG. 5 shows cross-sectional microtopography of nano-intumescent coatings containing different enhancers; as shown in fig. 5 (a), the fracture surface of pure EP without the reinforcing agent is relatively flat, indicating that the fracture is easily spread during the stress, which is characteristic of brittle failure; such flat fracture structures also more easily lead to heat penetration to the substrate; in fig. 5 (b), the addition of CS filler roughens the fracture surface, showing significant step-like wrinkles, which effectively increases the resistance and difficulty of external heat transfer inward; in fig. 5 (c), the CS/PAP filled EP shows a rough fracture surface similar to that of CS/EP, indicating that the coverage of the PAP layer does not destroy the good dispersibility of CS in EP; for the ZHS enhanced EP swell samples (fig. 5 (d)), a similar rough fracture surface with steps could be observed, however some unfriendly aggregates appeared in localized areas, indicating that the dispersion of pure ZHS in the EP matrix was limited; as shown in fig. 5 (e), the CS/pap@zhs filled EP had the same rough fracture surface and no significant aggregate formation, indicating that CS/PAP as a carrier could effectively improve the dispersion of ZHS in the resin matrix, strongly ensuring the positive contribution of the composite flame retardant to the fire resistance of the coating.
(5) The trend of the back temperature change of the different expansion coatings in the combustion process is shown in fig. 6; the temperature of the back surface of the bare steel rapidly rises to more than 500 ℃ within 10 minutes after encountering a flame, which is fatal to the structural strength of the steel structure; after the EP is coated on the surface of the steel, the temperature rising rate is obviously reduced, and finally the temperature is kept at 261.2 ℃, thus proving the effective function of the expanded carbon; after CS filler is added into the epoxy resin, the back temperature of the epoxy resin is reduced to 223.1 ℃ due to the enhancement of CS on the barrier effect of residual carbon; for the CS/PAP/EP coating samples, the backside temperature was significantly reduced to 189.4℃which is mainly related to the P-C-N composite structure in the ATP structure, which favors carbon residue formation. For the EP composite expansion sample loaded with ZHS, the back temperature is 204.6 ℃, which is obviously lower than that of the CS/EP composite expansion sample, and is mainly caused by the gas phase-condensed phase composite flame retardant effect of the ZHS; of course, the undesirable dispersion also determines its relatively limited thermal resistance effect; the back temperature value of the EP expansion coating filled with the CS/PAP@ZHS composite reinforcing agent reaches the minimum value (171.9 ℃), and the highest thermal barrier effect is reflected; the results indicate that the composite structural reinforcement is very effective in improving the fire resistance of the intumescent coating.
(6) FIG. 7 shows the state of the expanded carbon after the sample is calcined in a high temperature furnace for 1 hour; it can be seen that there is a significant difference in the expanded focal height of the different nano-additive filled expanded coatings; the detailed expansion data are shown in table 2 and fig. 8; the expansion height and expansion rate of the EP sample without nanofiller were relatively low, 6.4mm and 5.04mm, respectively, indicating poor expansibility; after filling with 3% CS nanoparticles, the expansion height and expansion rate increased to 10.6mm and 8.09mm, respectively, since CS remaining after high temperature prevented the discharge of degradants and vapors from the gas source, thereby improving the expansion capacity of the sample. The swelling effect of the EP composite coating filled with CS/PAP is more pronounced (18.2 mm and 13.79 mm), which can be traced back to the fact that the phosphate generated by the phosphorus-containing groups in the PAP structure promotes coke formation; this is advantageous in capturing the gas generated by the expanding component in the coke and improving the foaming effect; for ZHS/EP expansion samples, due to the gas-phase foaming effect of water molecules generated by decomposition of ZHS at high temperature, the ZHS has higher combustion expansion characteristics (14.5 mm,11.24 mm), and meanwhile, metals Zn and Sn in the structure are also important for promoting the growth of carbon; in contrast, the CS/pap@zhs filled EP composite coating exhibited the most excellent expansion characteristics (an expansion height of 23.1mm, an expansion ratio of 17.63) due to the composite reinforcing effect of CS, PAP and ZHS.
TABLE 2 expansion data for the different coatings
(7) The tendency of the prepared composite expansion sample containing different nano flame retardants to generate smoke in the combustion process is shown in fig. 9; in fig. 9 (a), the light absorption value of the pure epoxy resin is always higher than that of the composite expansion sample added with nanofiller in 0-240 seconds, which means its highest smoke emission; the smoke density grade obtained is shown in fig. 9 (b); the smoke density grade of the pure epoxy resin is highest, and the smoke density grade of the composite coating sample added with the nano filler has a descending trend, wherein CS/EP is 58.4, CS/PAP/EP is 48.1, ZHS/EP is 51.9, CS/PAP@ZHS is 40.7; a decrease in the CS/EP smoke density rating indicates that the addition of CS can reduce smoke generation; coating of PAP further reduces smoke rating, mainly because phosphates in PAP break free radical chain reactions during combustion, thereby reducing further degradation of the cracking material; the reason why the EP smoke grade value of ZHS filling is lower can be explained as that Zn and Sn induce more organic molecules to be converted into stable coke, thereby reducing the generation of smoke to the greatest extent; the lowest smoke density rating of CS/PAP@ZHS/EP is related to the additive effect of the combined action of CS, PAP and ZHS.
(8) The crystal structure of the carbon layer after combustion of the composite coating of EP, CS/EP, CS/PAP/EP, ZHS/EP and CS/PAP@ZHS/EP was characterized by X-ray diffractometer (XRD), and the results are shown in FIG. 10; a broad weak peak at 24.7 ° was present in all carbon residues, consistent with amorphous carbon signaling; furthermore, a series of sharp characteristic diffraction signals for ZHS were not found in EP intumescent coating carbon residue filled with ZHS and CS/pap@zhs enhancer, whereas two diffraction signals belonging to Zinc Stannate (ZS) were captured at 33.5 ° and 58.5 °, indicating that ZHS was converted to ZS during calcination; fortunately, the conversion process releases a certain amount of water molecules, so that the concentration of the combustible gas can be diluted and part of heat of a combustion area can be taken away; meanwhile, the residue of ZS powerfully guarantees the catalytic carbonizing effect of Zn and Sn in the combustion process.
(9) FIG. 11 shows SEM images of coke produced by the burning of different coatings; the carbon residue surface of pure EP (fig. 11 (a)) has large and obvious cavity defects, consistent with its worst flame/heat barrier effect; the introduction of CS filler (fig. 11 (b)) reduced the large void defects on the residual coal surface, but still captured many traces of cracks; the addition of CS/PAP enhancer resulted in a significant improvement in the integrity of the entire remaining char (FIG. 11 (c)), and only a few small cracks could be observed, which is indispensible from the role of phosphorus-containing species in PAP in promoting more char production; the number of residual Jiao Biaomian cracks of the ZHS/EP composite intumescent coating increased compared to CS/PAP/EP (FIG. 11 (d)), which is associated with poor dispersion of unmodified ZHS in the coating system; finally, the residual coke of CS/pap@zhs (fig. 11 (e)) presents an almost defect-free, complete surface, which determines its most excellent barrier effect to heat, which is highly consistent with the results of previous refractory experiments; as is evident from EDS-Mapping (FIG. 11 (f-i)) of CS/PAP@ZHS/EP carbon residue, C, N, zn and Sn are uniformly dispersed on the surface, demonstrating that the residual zinc stannate is uniformly dispersed in the carbon layer, which has an important effect on the strength and barrier effect of the carbon residue.
Claims (3)
1. The preparation method of the PAP activated carbon sphere-based water-based epoxy intumescent fireproof coating comprises the following steps:
(1) Preparing a base material;
Dispersing Melamine (MEL), pentaerythritol (PER) and ammonium polyphosphate (APP) in a proper amount of deionized water, and fully mixing under intense stirring; then adding the aqueous epoxy emulsion and the curing agent into the mixed solution of melamine, pentaerythritol and ammonium polyphosphate, and continuously stirring for 15-20 minutes to obtain an aqueous expansion epoxy resin base material;
(2) Preparing a CS/PAP@ZHS composite flame retardant;
Glucose is completely dissolved in 100mL of deionized water, and the glucose solution is poured into a hydrothermal reaction kettle and subjected to hydrothermal reaction for 24 hours at 180 ℃; next, carbon Spheres (CS) were obtained by mixing washing with ethanol and deionized water, and centrifuging; then, ultrasonically dispersing the prepared CS into 100mL of deionized water, and simultaneously adding dopamine hydrochloride and adenosine triphosphate into CS dispersion under the condition of continuous stirring; and the pH was adjusted to 8.5 with 1mol/L sodium hydroxide solution, and the reaction was continued at room temperature for 16 hours to obtain PAP-modified CS (CS/PAP hybrid); continuously dispersing the CS/PAP hybrid in 100mL of deionized water by ultrasonic, sequentially adding zinc sulfate and sodium stannate into the mixed solution of the CS/PAP hybrid, and reacting for 4 hours; finally, the suspension is repeatedly centrifuged and washed to obtain CS/PAP@ZHS composite flame retardant;
(3) A preparation method of PAP activated carbon sphere-based water-based epoxy intumescent fireproof coating;
The CS/PAP@ZHS composite flame retardant is weighed and mixed with the base material, and a uniform coating system is formed through mechanical stirring; then brushing the uniformly mixed water-based intumescent fire-retardant coating on the surface of the steel plate with the size of 10 multiplied by 10cm subjected to sand blasting pretreatment, curing for 7 days at normal temperature after brushing, and baking for 3 days at 40 ℃ to obtain the PAP activated carbon sphere-based water-based epoxy intumescent fire-retardant coating.
2. The method for preparing the PAP activated carbon sphere-based aqueous epoxy intumescent fire protection coating according to claim 1, wherein the concentration of glucose in the step (2) is 150-200g/L, and the content of CS in CS dispersion is 2-7mg/mL; the mass ratio of the dopamine hydrochloride to the adenosine triphosphate is 1:2-3; the mass fraction of the CS/PAP@ZHS composite flame retardant in the step (3) is 2.0% -5.0%.
3. A PAP activated carbon sphere-based waterborne epoxy intumescent fire-resistant coating prepared by the method of any of claims 1-2.
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