CN117736562A - Bagasse fiber reinforced biodegradable composite material and preparation method thereof - Google Patents
Bagasse fiber reinforced biodegradable composite material and preparation method thereof Download PDFInfo
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- CN117736562A CN117736562A CN202410181768.7A CN202410181768A CN117736562A CN 117736562 A CN117736562 A CN 117736562A CN 202410181768 A CN202410181768 A CN 202410181768A CN 117736562 A CN117736562 A CN 117736562A
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- 241000609240 Ambelania acida Species 0.000 title claims abstract description 355
- 239000010905 bagasse Substances 0.000 title claims abstract description 355
- 239000000835 fiber Substances 0.000 title claims abstract description 234
- 239000002131 composite material Substances 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 177
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 142
- 229920005989 resin Polymers 0.000 claims abstract description 100
- 239000011347 resin Substances 0.000 claims abstract description 100
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 94
- 238000002156 mixing Methods 0.000 claims abstract description 92
- 238000001035 drying Methods 0.000 claims abstract description 67
- 229920001896 polybutyrate Polymers 0.000 claims abstract description 65
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 56
- 239000003513 alkali Substances 0.000 claims abstract description 50
- 238000003756 stirring Methods 0.000 claims abstract description 47
- 239000002243 precursor Substances 0.000 claims abstract description 42
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 39
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 36
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 35
- 239000012266 salt solution Substances 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920000520 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Polymers 0.000 claims abstract description 28
- 239000000725 suspension Substances 0.000 claims abstract description 27
- 239000000945 filler Substances 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 26
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- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
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- 238000000227 grinding Methods 0.000 claims abstract description 17
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 11
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims abstract description 8
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- 238000000034 method Methods 0.000 claims description 42
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
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- 238000004880 explosion Methods 0.000 claims description 20
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- 239000000463 material Substances 0.000 claims description 18
- 238000000967 suction filtration Methods 0.000 claims description 16
- 239000006228 supernatant Substances 0.000 claims description 16
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 13
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 12
- 238000007909 melt granulation Methods 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 9
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
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- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
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- 229920000642 polymer Polymers 0.000 description 69
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
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- 239000002994 raw material Substances 0.000 description 7
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 7
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- 241000196324 Embryophyta Species 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
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- 230000004888 barrier function Effects 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
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- 235000015334 Phyllostachys viridis Nutrition 0.000 description 3
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- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a bagasse fiber reinforced biodegradable composite material and a preparation method thereof, comprising the following steps: soaking bagasse in a modified solution composed of alkali and inorganic salt to obtain modified bagasse powder, and soaking in a silane coupling agent solution to obtain modified bagasse fiber; mixing montmorillonite suspension with ferric salt solution to form precursor solution, stirring and heating to obtain reaction solution, standing, layering, washing and drying to obtain inorganic modified montmorillonite; cetyl trimethyl ammonium bromide and n-butanol are dissolved in n-hexane, and inorganic modified montmorillonite and calcium salt solution are added into the mixed solution to form microemulsion; mixing and stirring the carbonate solution and the microemulsion to obtain a reaction solution, and standing for layering, washing, drying and grinding to obtain a modified reinforcing filler; melting and granulating the modified bagasse fibers, the modified reinforcing filler and the PBAT resin to obtain filler master batches; and melting and granulating the filler master batch, the PHBV resin and the PBAT resin to obtain the biodegradable composite material.
Description
Technical Field
The invention belongs to the technical field of biodegradable materials, and relates to a bagasse fiber reinforced biodegradable composite material and a preparation method thereof.
Background
Bagasse is a main waste byproduct of the sugar industry, is fiber residue remained after the juice extraction of the sugarcane, and accounts for about 24% -27% of the total mass of the sugarcane, and 2-3 tons of bagasse can be produced every ton of sucrose produced. Bagasse is one of the largest yield plant fibers in agricultural waste worldwide, and the annual global bagasse yield is statistically up to hundreds of millions of tons. At present, the bagasse has limited resource conversion and utilization technology, most of the bagasse is directly used as fuel for incineration or accumulation and discard, only a small amount of the bagasse is used for pulping and papermaking or is converted into biomass energy, the application path range is narrow, the utilization rate is low, and the bagasse not only causes great waste of resources, but also causes the problem of environmental pollution. The bagasse comprises cellulose (32-45%), hemicellulose (20-32%), lignin (17-32%), ash (1-9%) and small amounts of other components. Although the wood and bamboo are lower than the cellulose content and the fiber form is shorter, the wood and bamboo fiber is higher than the wheat straw fiber and rice straw fiber of other agricultural wastes such as wheat straw fiber and rice straw fiber, and the wood and bamboo fiber is used as the waste after sugar making of sugar factories, and has the characteristic of concentrated raw materials.
The mechanical properties of the plant fiber reinforced composite material are influenced by the strength of the fibers, the size of the fiber particle size, the interfacial compatibility between the fibers and the matrix and other factors, wherein the interfacial compatibility is a key factor influencing the mechanical properties, stress is transmitted between the fibers and the matrix through an interface, and good interfacial adhesion is required to achieve the optimal reinforcing effect. However, the fiber structure contains a large amount of hydrophilic polar groups, and has poor interfacial compatibility and adhesion with the hydrophobic nonpolar plastic matrix. At the same time, the cellulose in the plant fiber is coated with a large amount of non-cellulose substances, and the existence of the components makes the fiber and the matrix have poor wettability, so that the interface combination between the two components is hindered; the fiber is easy to agglomerate and have poor dispersibility under the action of hydrogen bonds in the processing process, so that the reinforcing effect of the fiber is greatly reduced. Therefore, improving the interfacial compatibility between the fibers and the matrix is a key to improving the comprehensive performance of the plant fiber reinforced composite material.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a bagasse fiber reinforced biodegradable composite material and a preparation method thereof.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a bagasse fibre reinforced biodegradable composite material, the method comprising:
soaking bagasse in a modified solution consisting of alkali and inorganic salt, mixing, stirring, heating in a water bath, performing suction filtration to obtain modified bagasse, and performing freeze drying and grinding and crushing on the modified bagasse to obtain modified bagasse powder; soaking the modified bagasse powder in a silane coupling agent solution, performing suction filtration, washing and drying to obtain wet bagasse, and performing steam explosion on the wet bagasse to obtain modified bagasse fibers;
dispersing montmorillonite in deionized water to form montmorillonite suspension, and mixing the montmorillonite suspension with ferric salt solution to form precursor solution; dropwise adding an alkali solution into the precursor solution to adjust the pH value of the precursor solution, stirring and heating the precursor solution to obtain a reaction solution, standing and layering the reaction solution to obtain a precipitate and a supernatant, and washing and drying the precipitate to obtain inorganic modified montmorillonite;
(III) dissolving cetyl trimethyl ammonium bromide and n-butanol in n-hexane, uniformly mixing, adding the inorganic modified montmorillonite and calcium salt solution obtained in the step (II) into the mixed solution, and uniformly mixing to form microemulsion; mixing and stirring carbonate solution and microemulsion to obtain a reaction solution, standing and layering the reaction solution to obtain a precipitate and supernatant, and washing, drying and grinding the precipitate to obtain a modified reinforcing filler;
Uniformly mixing the modified bagasse fiber obtained in the step (I), the modified reinforcing filler obtained in the step (III) and the first PBAT resin, then injecting the mixture into a first double-screw extruder, and obtaining filler master batch after melting and granulating; and uniformly mixing the filler master batch, PHBV resin and second PBAT resin, then injecting the mixture into a second double-screw extruder, and performing melt granulation to obtain the biodegradable composite material.
According to the invention, PHB V resin is used as a matrix, PBAT resin is used as a toughening material, and modified bagasse fiber and modified reinforcing filler are used as reinforcing materials, so that the composite material which has excellent mechanical properties and can be completely biodegraded is prepared.
Polyadipic acid/butylene terephthalate (PBAT resin) is a synthetic polymer based on petrochemical resources, which is a fully biodegradable aliphatic-aromatic copolyester formed by esterification and polycondensation of 1, 4-butanediol with adipic acid and terephthalic acid. The PBAT resin is a random polymer, and can not form obvious crystallization, so that the PBAT resin has the physical characteristics of wide melting point and high flexibility (the elongation at break can reach more than 600 percent), belongs to an elastomer material with excellent ductility, and has lower mechanical strength.
PHBV resin is one of the most promising bioplastic in commercial application, has the advantages of high strength, good barrier property, high degradation rate and the like, but is brittle, poor in thermal stability and high in material cost, so that the wide application of the PHBV resin is limited; but the PBAT resin has good flexibility and thermal stability, but has lower mechanical strength and poorer gas barrier property. The PHBV resin and the PBAT resin have complementarity in material performance, and the composite material prepared by blending the PHBV resin and the PBAT resin has the advantages of both, can improve the defect of the PHBV resin while keeping the complete biodegradability, and improves the comprehensive performance of the composite material, but the production cost is still high. The bagasse is used as agricultural waste, has the advantages of abundant resources, low price, easy obtainment, low density, high specific strength and the like, is added into resin raw materials for melt blending and extrusion granulation, so that the biodegradable composite material is prepared, the bagasse can be used as a reinforcing material to improve the rigidity and crystallization performance of the composite material, the comprehensive utilization of bagasse resources can be realized, the added value of agricultural products is increased, the burden of shortage of wood resources is reduced, the production cost of the composite material is reduced, and the composite material meets the current social requirements and economic development, and has important significance for developing the composite material with high performance, low cost and environmental friendliness.
The untreated bagasse surface is covered with low molecular components such as pectin, lignin, hemicellulose and the like, so that the interfacial compatibility with a polymer matrix is poor, and the mechanical property of the finally prepared composite material is reduced; in order to solve the problem of poor compatibility of the bagasse fibers and the polymer matrix, the bagasse is chemically modified to reduce the surface polarity of the bagasse fibers, so that the mechanical reinforcing effect of the bagasse fibers can be better realized, and the comprehensive performance of the composite material is further improved. According to the invention, through the combined modification of alkali treatment, inorganic salt treatment and silane coupling agent treatment, the interface compatibility between the modified bagasse fiber and the polymer matrix is better, the modified bagasse fiber can be completely coated in the polymer matrix, the interface combination between the modified bagasse fiber and the polymer matrix is tighter, and the mechanical reinforcing effect of the bagasse fiber can be fully exerted.
The invention carries out the combined modification treatment of alkali and inorganic salt on bagasse, and the synergistic effect of the alkali and the inorganic salt is shown as follows: (1) The inorganic salt can enable lignin, hemicellulose, pectin, protein and other impurities on the surface of the bagasse to fall off from the surface of the bagasse, and the fallen lignin, hemicellulose, pectin, protein and other impurities are dissolved under the action of alkali; the direct dissolution of bagasse fibers caused by excessive alkali can be effectively avoided by a modification mode of firstly shedding and then dissolving. (2) Inorganic salt can permeate into a molecular chain lattice layer of the bagasse to destroy the wrapping structure of the bagasse, so that the bagasse fibers are completely exposed, and alkali can generate a chemical etching effect on the surfaces of the bagasse fibers along with the exposure of the bagasse fibers, so that the surface roughness of the bagasse fibers is improved, the interface contact area of the bagasse fibers and a polymer matrix is increased, and the mechanical meshing effect between the bagasse fibers and the polymer matrix is improved; meanwhile, the alkali can also react with hydroxyl groups on the surfaces of the bagasse fibers, so that the number of hydroxyl functional groups on the surfaces of the bagasse fibers is reduced, the surface polarity of the bagasse is reduced, the dispersion of the bagasse fibers in the polymer matrix is more uniform, the contact area between the bagasse fibers and the polymer matrix is increased, and further the interfacial effect and the bonding effect between the bagasse fibers and the polymer matrix are enhanced. However, as the degree of fibrillation of the bagasse after being soaked in alkali liquor is higher, the mechanical strength of the bagasse fiber is reduced due to high fibrillation, which is not beneficial to the improvement of the impact strength of the composite material.
The invention further adopts the silane coupling agent to modify on the basis of alkali treatment, so that the chemical bonding between bagasse fibers and a polymer matrix can be enhanced, and the silane coupling agent is a micromolecular surface modifier, so that the interfacial bonding strength between the bagasse fibers and the polymer matrix can be enhanced through the actions of chemical bonds and hydrogen bonds, thereby providing good interfacial affinity; in addition, the water solution of the silane coupling agent has extremely strong permeability and can permeate all gaps among the bagasse fibers, so that the whole surface of the bagasse fibers is further infiltrated, and the silane coupling agent and the surface of the bagasse fibers are kept in good infiltration contact; the silanol is formed after the alkoxy groups in the silane coupling agent are hydrolyzed, the silanol can perform a chemical bond action with hydroxyl groups in the bagasse fibers, and an organosilane molecular layer is formed on the surfaces of the bagasse fibers, so that the water absorbability of the bagasse fibers is reduced, the surface polarity of the bagasse fibers is reduced, the dispersibility of the bagasse fibers in a polymer matrix is obviously improved, the agglomeration of the bagasse fibers is effectively prevented, the defect number and the defect size at the interface of the bagasse fibers and the polymer matrix are reduced, and when the composite material is impacted, most of impact energy is consumed through good interface compatibility, so that the impact toughness of the finally prepared composite material is improved, and the impact strength of the composite material is improved. Therefore, the invention can effectively solve the problem of reduced impact strength caused by alkali treatment by modifying the silane coupling agent and utilizing the interface affinity effect of the silane coupling agent.
In order to improve the dispersibility of montmorillonite in a polymer matrix and improve the interfacial compatibility between the montmorillonite and the polymer matrix, the invention adopts ferric salt and CTAB to carry out inorganic modification and organic modification on the montmorillonite, and the modified montmorillonite can be uniformly adsorbed on the skeleton structure of the modified bagasse fiber in the melt extrusion process of the modified reinforcing filler and the modified bagasse fiber to form the skeleton supporting structure of the modified bagasse fiber/modified reinforcing filler, thereby greatly improving the impact strength of the composite material.
According to the invention, ferric salt is used as an inorganic modifier to carry out inorganic modification on montmorillonite, on one hand, iron ions in the ferric salt are replaced with cations on the surface of the montmorillonite, so that the interlayer spacing of the montmorillonite is increased; on the other hand, fe produced by oxidation reaction of iron salt under alkaline condition 3 O 4 Can be loaded between the montmorillonite layers to swell the montmorillonite, further increase the interlayer spacing, generate a large number of active surface adsorption sites and provide a basis for the subsequent adsorption of CTAB.
On the basis of inorganic modification, the invention organically modifies the montmorillonite by CTAB to hydrophobize the surface, after introducing CTAB into the montmorillonite layers, the interlayer spacing of the montmorillonite is increased, and the montmorillonite has good expansion performance, meanwhile, the interfacial polarity between the montmorillonite and the calcium carbonate particles is improved, a montmorillonite lamellar structure capable of containing larger calcium carbonate particles is formed, and sufficient active sites are provided for subsequent crystal grain nucleation of the calcium carbonate particles. In addition, the surface hydrophilicity of the montmorillonite which is not subjected to organic modification treatment is stronger, and the dispersion of the montmorillonite in PBAT resin melt is not facilitated. In addition, the stronger interaction between CTAB molecules and calcium carbonate particles can effectively prevent calcium carbonate crystals from growing, so that the particle size of the prepared calcium carbonate particles is smaller, and the montmorillonite and the calcium carbonate particles are protected by CTAB in a solution system and are in a stable state, so that the agglomeration is not caused, and the prepared montmorillonite/calcium carbonate modified reinforcing filler can be stably stored for a long time.
According to the invention, when the montmorillonite is modified, the modified reinforcing filler compounded by the modified montmorillonite and the calcium carbonate particles is prepared by a microemulsion method, the nucleation of calcium carbonate grains can be effectively promoted by virtue of active surface adsorption sites formed between montmorillonite layers after modification, meanwhile, the growth of the calcium carbonate grains can be effectively inhibited by utilizing a narrow area between montmorillonite layers, the growth of the calcium carbonate grains is inhibited by accelerating the nucleation of the calcium carbonate grains, and the nano-grade calcium carbonate particles can be obtained, wherein the particle size of the calcium carbonate particles can be controlled between a few nanometers and tens of nanometers.
In the step (i), the mass fraction of the alkali in the modified solution is 1 to 5wt%, for example, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt%, 3.0wt%, 3.5wt%, 4.0wt%, 4.5wt% or 5.0wt%, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Bagasse contains a large amount of hemicellulose and lignin, wherein the lignin is a network structure and serves as a framework to support the cellulose and the hemicellulose, and the hemicellulose serves as a binder to bond various components together. Therefore, when the bagasse which is not modified is added into the composite material, the cellulose content in the bagasse fiber is low, and the bagasse fiber is coated by hemicellulose, lignin and pectin, so that the interfacial adhesion with a polymer matrix is poor, and the advantage of high strength of the bagasse fiber can not be well exerted. The bagasse after alkali treatment and inorganic salt treatment removes hemicellulose and lignin, so that the cellulose is fully released and exposed, phenolic hydroxyl groups on the cellulose can well act with a polymer matrix, and the interfacial binding force between bagasse fibers and the polymer matrix is enhanced, so that the mechanical property of the finally prepared composite material is obviously improved.
The tensile property and the bending property of the composite material are in a change trend of increasing and then decreasing with the increase of the mass fraction of alkali in the modified solution. The invention particularly limits that the mass fraction of alkali in the modified solution is 1-5wt%, and the low-concentration alkali treatment can remove impurities on the surface of bagasse without damaging the surface structure of bagasse; meanwhile, a certain chemical etching effect can be generated on the surface of the bagasse, so that the specific surface area of the bagasse is increased, the contact area of the bagasse and the polymer matrix is further increased, the mechanical meshing effect between the bagasse fibers and the polymer matrix is promoted, and the interfacial adhesion between the bagasse fibers and the polymer matrix is improved. However, excessive alkali treatment weakens or even damages the structure of the bagasse fiber, when the mass fraction of alkali in the modifying solution exceeds 5wt%, fiber fragments on the surface of the bagasse fiber are peeled off, the integral structure of the bagasse fiber becomes loose, holes and even cracks start to appear, larger gaps are generated, the mechanical strength of the bagasse fiber is reduced, and the mechanical reinforcing effect of the bagasse fiber cannot be effectively exerted.
In addition, the metal ions in the alkaline solution are typically present as "hydrated ions" which are more advantageous for entering the bagasse fibre crystallization zone, and the alkaline treatment can cause swelling of the bagasse fibres and weakening of the hydroxyl binding forces between the bagasse fibre macromolecules. When the mass fraction of the alkali in the modified solution is in the range of 1-5wt%, the swelling of the bagasse fiber crystallization zone can be effectively promoted. When the mass fraction of the alkali exceeds 5wt%, the radius of the formed hydrated ions is rather reduced due to the excessive density of the metal ions in the alkali, so that the degree of swelling of the bagasse fibers is reduced, resulting in an increase in the polarity of the bagasse fibers.
In some alternative examples, the base includes sodium hydroxide and/or potassium hydroxide.
In some alternative examples, the mass fraction of the inorganic salt in the modifying solution is 2-3 wt%, for example, 2.0wt%, 2.1wt%, 2.2wt%, 2.3wt%, 2.4wt%, 2.5wt%, 2.6wt%, 2.7wt%, 2.8wt%, 2.9wt%, or 3.0wt%, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The invention particularly limits that the mass fraction of the inorganic salt in the modified solution is 2-3wt%, the relative hydrogen bond strength among bagasse fibers gradually decreases along with the increase of the mass fraction of the inorganic salt, and when the mass fraction of the inorganic salt in the modified solution is lower than 2wt%, the degree of the decrease of the relative hydrogen bond strength among bagasse fibers is not obvious. When the mass fraction of the inorganic salt in the modified solution is within the range of 2-3wt%, the relative content of metal ions in the modified solution is increased, so that the modified solution is beneficial to more rapidly and densely penetrating into bagasse, more hydroxyl groups in bagasse fibers are subjected to complexation reaction with the metal ions, hydrogen bonds of the bagasse fibers are destroyed, the relative hydrogen bond strength among the bagasse fibers is rapidly reduced, part of impurity molecules fall off or are dissolved in the inorganic salt solution, and the relative content of cellulose in the bagasse is increased; meanwhile, due to weakening of hydrogen bond action, bagasse fibers can be well dispersed in the polymer matrix, and good interface effect between the bagasse fibers and the polymer matrix can help the composite material to complete stress transmission, so that the tensile strength of the composite material is greatly improved. When the mass fraction of the inorganic salt in the modified solution exceeds 3wt%, the rate of decrease in the relative hydrogen bond strength between bagasse fibers gradually slows down. This is because, when the mass fraction of the inorganic salt is too high, most of the hydroxyl groups in the bagasse fibers have been completely reacted with the metal ions, and the number of unreacted hydroxyl groups gradually decreases, and thus the decrease in the relative hydrogen bond strength between the bagasse fibers is retarded.
In addition, when the mass fraction of the inorganic salt in the modified solution reaches 2wt%, the wax on the surface of the bagasse falls off, short crystallites are exposed out, a fibrillation phenomenon starts to appear, the surface of the bagasse fiber becomes rough, and a groove mark structure appears. Along with the continuous improvement of the mass fraction of the inorganic salt, the surface of the bagasse fiber has more and deeper groove marks, which can increase the contact area between the bagasse fiber and the polymer matrix, thereby enhancing the mechanical meshing effect between the bagasse fiber and the polymer matrix and further improving the comprehensive performance of the composite material. When the mass fraction of the inorganic salt in the modified solution exceeds 3wt%, although the relative hydrogen bond strength is low at this time, too high a concentration of metal ions may cause excessive and deepening of the groove marks on the surface of the bagasse fibers, causing serious erosion to the bagasse to cause fiber defects, which may impair the mechanical strength of the bagasse fibers to some extent, and simultaneously, the bagasse fibers may have a reduced stress transmitting ability in the polymer matrix, be liable to fiber breakage and fracture, and may have a negative effect on the tensile properties and impact resistance of the finally produced composite material.
In some alternative examples, the inorganic salt includes any one or a combination of at least two of magnesium chloride, zinc chloride, aluminum chloride, calcium chloride, or sodium chloride.
In some alternative examples, the ratio of bagasse to the modifying solution is 1g (100-200) mL, which may be, for example, 1g:100mL, 1g:110mL, 1g:120mL, 1g:130mL, 1g:140mL, 1g:150mL, 1g:160mL, 1g:170mL, 1g:180mL, 1g:190mL, or 1g:200mL, but is not limited to the recited values, as are other non-recited values within the range of values.
In some alternative examples, the mixing time is 0.5-1.5 h, for example, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1.0h, 1.1h, 1.2h, 1.3h, 1.4h or 1.5h, but not limited to the recited values, and other non-recited values within the range are equally applicable.
The untreated bagasse has rugged surface, and is coated with a layer of waxy substance, and after the bagasse is subjected to surface modification by adopting a modification solution composed of alkali and inorganic salt, the waxy substance coated on the bagasse surface can be eluted. When the mixing and stirring time reaches more than 0.5h, the metal ions in the modified solution have enough time to carry out complexation reaction with hydroxyl groups in bagasse fibers, so that most impurities on the surface of bagasse are already shed, and a large number of obvious groove marks appear. With the extension of the mixing and stirring time, the more the hydrogen bond of the bagasse fiber is broken, the lower the surface energy of the bagasse fiber is, which is more beneficial to improving the interfacial property between the bagasse fiber and the polymer matrix and improving the dispersion degree of the bagasse fiber in the polymer matrix. When the mixing and stirring time exceeds 1.5 hours, the relative hydrogen bond strength among bagasse fibers is not obviously changed, and the surface morphology of the bagasse fibers is also not obviously changed. This means that, with the extension of the mixing and stirring time, the more uniformly the bagasse fibers are dispersed in the polymer matrix, the larger the contact area is, the stronger the mechanical meshing effect is, the higher the stress transferring efficiency is, and the more obvious the tensile strength of the composite material is improved, but the effect is better when the mixing and stirring time is 1.5h, and the comprehensive performance of the composite material is not obviously improved even if the mixing and stirring time is continuously prolonged.
In some alternative examples, the water bath heating temperature is 50-60 ℃, such as 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃ or 60 ℃, but not limited to the recited values, and other non-recited values within the range are equally applicable.
The relative hydrogen bond strength between bagasse fibers gradually decreases along with the increase of the water bath heating temperature, when the water bath heating temperature is increased to 50 ℃, the diffusion speed and the permeation speed of metal ions in the modified solution in bagasse are obviously improved, the probability of effective combination of the metal ions and hydroxyl groups on the surface of the bagasse fibers is improved, and the complexation reaction occurs more frequently, so that the hydrogen bond is broken, and the relative hydrogen bond strength between the bagasse fibers is weakened; in addition, along with the rising of water bath heating temperature, the impurity on bagasse surface is further removed, and bagasse fibrillation phenomenon is more obvious, and the ditch mark on the bagasse fiber surface that forms increases and deepens, and bagasse fiber's surface roughness further promotes, can promote the mechanical meshing effect between bagasse fiber and the polymer matrix, improves combined material's comprehensive properties.
In some alternative examples, the freeze-drying temperature is-60 to-30 ℃, such as-60 ℃, -58 ℃, -56 ℃, -54 ℃, -52 ℃, -50 ℃, -48 ℃, -46 ℃, -44 ℃, -42 ℃, -40 ℃, -38 ℃, -36 ℃, -34 ℃, -32 ℃, or-30 ℃, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In some alternative examples, the freeze-drying time is 5-6 h, for example, 5.0h, 5.1h, 5.2h, 5.3h, 5.4h, 5.5h, 5.6h, 5.7h, 5.8h, 5.9h or 6.0h, but not limited to the recited values, and other non-recited values within the range are equally applicable.
In some alternative examples, the fineness of the modified bagasse powder is 200-300 mesh, for example, 200 mesh, 210 mesh, 220 mesh, 230 mesh, 240 mesh, 250 mesh, 260 mesh, 270 mesh, 280 mesh, 290 mesh, or 300 mesh, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferred embodiment of the present invention, in the step (I), the mass fraction of the silane coupling agent solution is 5 to 8wt%, for example, 5.0wt%, 5.2wt%, 5.4wt%, 5.6wt%, 5.8wt%, 6.0wt%, 6.2wt%, 6.4wt%, 6.6wt%, 6.8wt%, 7.0wt%, 7.2wt%, 7.4wt%, 7.6wt%, 7.8wt% or 8.0wt%, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The invention can improve the interfacial compatibility of the composite material by carrying out the combined surface modification treatment on the bagasse by alkali and inorganic salt, because the removal of non-cellulose substances on the surface of the bagasse fiber and the increase of roughness promote the physical combination between the bagasse fiber and the polymer matrix, but the chemical structure and the attribute of the surface of the bagasse fiber are not changed, so the modification effect on the bagasse is not obvious. The silane coupling agent is a common interface modifier, one end of the silane coupling agent after hydrolysis can react with hydroxyl on the surface of the fiber to be grafted on the surface of the bagasse fiber, and the other end of the silane coupling agent can react with the polymer matrix to be grafted on the polymer matrix, so that the silane coupling agent can be used as a molecular bridge between the bagasse fiber and the polymer matrix, the chemical bonding between the bagasse fiber and the polymer matrix is enhanced, and the interface compatibility between the bagasse fiber and the polymer matrix can be remarkably improved.
Because the bagasse which is not treated by alkali and inorganic salt contains hemicellulose, lignin and other non-cellulose substances, the hemicellulose and the lignin act as an adhesive and a filler to wrap the cellulose, the structure is unfavorable for the infiltration and reaction of the silane coupling agent on bagasse fibers, and the improvement of the mechanical property of the composite material is limited. Therefore, before the silane coupling agent is treated, after hemicellulose and lignin in bagasse are removed through alkali and inorganic salt treatment, the silane coupling agent is enabled to infiltrate the surface of bagasse fiber more easily, the silane coupling agent reacts with hydroxyl on the surface of the bagasse fiber and forms chemical bonds to graft on the surface of the bagasse fiber, so that the polarity of the bagasse fiber is reduced, the interfacial compatibility of the bagasse fiber and a polymer matrix is improved better, and stress transfer can be effectively realized under the action of external force.
The mechanical strength of the composite material is in a change trend of rising and then reducing along with the increase of the mass fraction of the silane coupling agent solution, the invention particularly limits the mass fraction of the silane coupling agent solution to 5-8wt%, because the silane coupling agent cannot completely react with bagasse fibers when the content of the silane coupling agent is lower than 5wt%, and the quantity of the silane coupling agent grafted on the surface of the bagasse fibers is continuously increased along with the increase of the mass fraction of the silane coupling agent solution, so that the interfacial compatibility between the bagasse fibers and a polymer matrix is improved; when the mass fraction of the silane coupling agent solution reaches 8wt%, the silane coupling agent exactly reacts with all hydroxyl groups on the surface of the bagasse fiber to form an ordered silane coupling agent monomolecular layer on the surface of the bagasse fiber in a grafting way, and the interface compatibility between the bagasse fiber and the polymer matrix is the best; when the mass fraction of the silane coupling agent solution exceeds 8wt%, the silane coupling agent is excessively hydrolyzed to form silanol, and the silanol is accumulated on the surface of the bagasse fiber to form a silanol polymolecular layer, so that the interfacial compatibility between the bagasse fiber and the polymer matrix is reduced, and the comprehensive performance of the composite material is affected.
In some alternative examples, the ratio of the modified bagasse powder to the silane coupling agent solution is 1g (100-200) mL, for example, 1g:100mL, 1g:110mL, 1g:120mL, 1g:130mL, 1g:140mL, 1g:150mL, 1g:160mL, 1g:170mL, 1g:180mL, 1g:190mL, or 1g:200mL, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In some alternative examples, the modified bagasse powder is soaked in the silane coupling agent solution for 2-3 hours, for example, 2.0 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours or 3.0 hours, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
In some alternative examples, the drying temperature is 70 to 80 ℃, such as 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, or 80 ℃, but the drying temperature is not limited to the recited values, and other non-recited values within the range are equally applicable.
In some alternative examples, the drying time is 1-2 h, for example, 1.0h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2.0h, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In some alternative examples, the moisture content of the dried wet bagasse is maintained at 20-30 wt%, for example, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, or 30wt%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In some alternative examples, the steam explosion pressure used in the steam explosion process is 1-5 MPa, for example, 1.0MPa, 1.5MPa, 2.0MPa, 2.5MPa, 3.0MPa, 3.5MPa, 4.0MPa, 4.5MPa or 5.0MPa, but is not limited to the values listed, and other values not listed in the range of values are equally applicable.
In some alternative examples, the dwell time of the steam explosion process is 40-50 min, for example, 40min, 41min, 42min, 43min, 44min, 45min, 46min, 47min, 48min, 49min or 50min, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In the step (ii), the mass fraction of the montmorillonite suspension is 5-10wt%, for example, 5.0wt%, 5.5wt%, 6.0wt%, 6.5wt%, 7.0wt%, 7.5wt%, 8.0wt%, 8.5wt%, 9.0wt%, 9.5wt% or 10.0wt%, but the present invention is not limited to the recited values, and other non-recited values in the range of values are applicable.
In some alternative examples, the concentration of the ferric salt solution is 0.1 to 0.5mol/L, for example, 0.1mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L or 0.5mol/L, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The invention particularly limits the concentration of the ferric salt solution to 0.1-0.5 mol/L, and when the concentration of the ferric salt solution is lower than 0.1mol/L, the montmorillonite can not be effectively intercalated and modified; when the concentration of the ferric salt solution is higher than 0.5mol/L, the surface skeleton of the montmorillonite is collapsed, and the pore canal of the montmorillonite is blocked by the agglomeration effect, so that the specific surface area, the pore diameter and the pore volume of the montmorillonite are reduced finally.
In some alternative examples, the volume ratio of the montmorillonite suspension to the ferric salt solution is 1 (1-2), for example, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1:2, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In some alternative examples, the iron salt in the iron salt solution comprises any one or a combination of at least two of ferric chloride, ferric sulfate, or ferric nitrate.
In the step (ii), alkali solution is added dropwise to the precursor solution to adjust the pH of the precursor solution to 10 to 11, and for example, 10, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9 or 11 may be used, but not limited to the listed values, and other non-listed values are applicable.
In some alternative examples, the precursor solution may be stirred for 1 to 5 hours, for example, 1.0 hour, 1.5 hours, 2.0 hours, 2.5 hours, 3.0 hours, 3.5 hours, 4.0 hours, 4.5 hours, or 5.0 hours, but not limited to the recited values, and other non-recited values within the range are equally applicable.
In some alternative examples, the heating temperature of the precursor solution is 50 to 60 ℃, for example, 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃ or 60 ℃, but the precursor solution is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
In some alternative examples, the reaction solution is allowed to stand for a period of 15-20 h, for example, 15h, 15.5h, 16h, 16.5h, 17h, 17.5h, 18h, 18.5h, 19h, 19.5h or 20h, but the reaction solution is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In some alternative examples, the drying temperature of the precipitate is 70-80 ℃, such as 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃ or 80 ℃, but not limited to the recited values, and other non-recited values within the range are equally applicable.
In some alternative examples, the drying time of the precipitate is 10 to 15 hours, for example, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours, 12.5 hours, 13 hours, 13.5 hours, 14 hours, 14.5 hours or 15 hours, but not limited to the recited values, and other non-recited values within the range are equally applicable.
In the preferred technical scheme of the invention, in the step (iii), the mass ratio of the cetyltrimethylammonium bromide, the n-butanol and the n-hexane is 1 (1-2): (8-9), for example, may be 1:1:8, 1:1.1:8.1, 1:1.2:8.2, 1:1.3:8.3, 1:1.4:8.4, 1:1.5:8.5, 1:1.6:8.6, 1:1.7:8.7, 1:1.8:8.8, 1:1.9:8.9 or 1:2:9, but not limited to the listed values, and other non-listed values in the range of values are equally applicable.
In some alternative examples, the mixing time of the cetyltrimethylammonium bromide, the n-butanol and the n-hexane is 20-30 min, for example, 20min, 21min, 22min, 23min, 24min, 25min, 26min, 27min, 28min, 29min or 30min, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In some alternative examples, the mixing temperature of the cetyltrimethylammonium bromide, the n-butanol and the n-hexane is 4-6 ℃, for example, 4.0 ℃, 4.2 ℃, 4.4 ℃, 4.6 ℃, 4.8 ℃, 5.0 ℃, 5.2 ℃, 5.4 ℃, 5.6 ℃, 5.8 ℃ or 6.0 ℃, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In some alternative examples, the mass ratio of the cetyltrimethylammonium bromide, the inorganic modified montmorillonite and the calcium salt solution is 1 (0.5-0.7): (0.1-0.3), for example, may be 1:0.5:0.1, 1:0.52:0.12, 1:0.54:0.14, 1:0.56:0.16, 1:0.58:0.18, 1:0.6:0.2, 1:0.62:0.22, 1:0.64:0.24, 1:0.66:0.26, 1:0.68:0.28 or 1:0.7:0.3, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In some alternative examples, the concentration of the calcium salt solution is 1 to 5mol/L, for example, 1.0mol/L, 1.5mol/L, 2.0mol/L, 2.5mol/L, 3.0mol/L, 3.5mol/L, 4.0mol/L, 4.5mol/L or 5.0mol/L, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In a preferred embodiment of the present invention, in the step (III), the concentration of the carbonate solution is 1 to 5mol/L, for example, 1.0mol/L, 1.5mol/L, 2.0mol/L, 2.5mol/L, 3.0mol/L, 3.5mol/L, 4.0mol/L, 4.5mol/L or 5.0mol/L, but the carbonate solution is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical ranges are applicable.
In some alternative examples, the mixing and stirring time of the carbonate solution and the microemulsion is 10-20 min, for example, 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min or 20min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
In some alternative examples, the rotational speed of mixing and stirring the carbonate solution and the microemulsion is 700-800 r/min, for example, 700r/min, 710r/min, 720r/min, 730r/min, 740r/min, 750r/min, 760r/min, 770r/min, 780r/min, 790r/min or 800r/min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
In some alternative examples, the time of standing and layering is 15-20 h, for example, 15.0h, 15.5h, 16.0h, 16.5h, 17.0h, 17.5h, 18.0h, 18.5h, 19.0h, 19.5h or 20.0h, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In some alternative examples, the drying temperature is 70 to 80 ℃, such as 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, or 80 ℃, but the drying temperature is not limited to the recited values, and other non-recited values within the range are equally applicable.
In some alternative examples, the drying time is 10 to 15 hours, for example, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours, 12.5 hours, 13 hours, 13.5 hours, 14 hours, 14.5 hours or 15 hours, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
In the step (iv), the mass ratio of the modified bagasse fiber to the modified reinforcing filler to the first PBAT resin is 1 (2-3) (5-6), for example, it may be 1:2:5, 1:2.1:5.1, 1:2.2:5.2, 1:2.3:5.3, 1:2.4:5.4, 1:2.5:5.5, 1:2.6:5.6, 1:2.7:5.7, 1:2.8:5.8, 1:2.9:5.9 or 1:3:6, but not limited to the listed values, and other non-listed values in the range of values are equally applicable.
Because bagasse has a lower density than other wood fibers, and is of the same mass, the volume of bagasse fibers can be much greater. Therefore, when the addition amount of the modified bagasse fiber is low, the mechanical reinforcing effect cannot be achieved, and the effective substitution of the polymer resin raw material cannot be achieved. With the increase of the addition amount of the modified bagasse fibers, the strength and the modulus of the composite material are gradually increased, and the strength and the modulus of the composite material are gradually increased with the increase of the addition amount of the modified bagasse fibers due to the acting force between the modified bagasse fibers and the interaction force between the modified bagasse fibers and the polymer matrix, so that the modified bagasse fibers can better dissipate stress in the polymer matrix, and meanwhile, the free movement of polymer molecules can be blocked, so that the molecular chain migration of the polymer molecules is limited, and the strength and the modulus of the composite material are higher and the deformation resistance of the composite material is higher. When the addition amount of the modified bagasse fiber is too high, the situation that the polymer matrix cannot fully cover the modified bagasse fiber easily occurs due to the large volume of the modified bagasse fiber, the bonding effect cannot be fully achieved, the surface of the composite material becomes rough gradually along with the improvement of the addition amount of the modified bagasse fiber, the phenomenon that the fusion bonding cannot be achieved starts to occur at the edge of a sample of the prepared composite material, and the area of an unmelted area is larger as the addition amount of the modified bagasse fiber is higher.
The invention particularly limits the mass ratio of the modified bagasse fiber to the modified reinforcing filler to the first PBAT resin to 1 (2-3) (5-6), particularly, the use amount of the first PBAT resin is higher, because when the use amount of the first PBAT resin is too low, the powder raw materials such as the modified bagasse fiber, the modified reinforcing filler and the like are excessively dispersed in the blending process, and the PBAT resin cannot form effective coating on the powder raw materials in the melt extrusion process, so that serious agglomeration phenomenon occurs between the powder raw materials; as the amount of the first PBAT resin increases, the PBAT resin forms a continuous phase and the filler master batch gradually transitions from brittle fracture to flexible yield.
In some optional examples, the mixing time of the modified bagasse fiber, the modified reinforcing filler, and the first PBAT resin is 30 to 40min, for example, 30min, 31min, 32min, 33min, 34min, 35min, 36min, 37min, 38min, 39min, or 40min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
In some optional examples, the rotational speed of the mixing process of the modified bagasse fiber, the modified reinforcing filler and the first PBAT resin is 800-1000 r/min, for example, 800r/min, 820r/min, 840r/min, 860r/min, 880r/min, 900r/min, 920r/min, 940r/min, 960r/min, 980r/min or 1000r/min, but not limited to the listed values, and other non-listed values in the range of values are equally applicable.
In some alternative examples, the extrusion temperature of the first twin-screw extruder is 160 to 170 ℃, for example 160 ℃, 161 ℃, 162 ℃, 163 ℃, 164 ℃, 165 ℃, 166 ℃, 167 ℃, 168 ℃, 169 ℃, or 170 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In some optional examples, the screw speed of the first twin-screw extruder is 100 to 200r/min, for example, 100r/min, 110r/min, 120r/min, 130r/min, 140r/min, 150r/min, 160r/min, 170r/min, 180r/min, 190r/min or 200r/min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
In the step (iv), the mass ratio of the filler masterbatch to the PHBV resin to the second PBAT resin is 1 (1.5-3) (2-3), for example, 1:1.5:2, 1:1.6:2.1, 1:1.8:2.2, 1:2:2.3, 1:2.2:2.4, 1:2.4:2.5, 1:2.6:2.6, 1:2.7:2.7, 1:2.8:2.8 or 1:3:3, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
The invention particularly limits the mass ratio of the filler master batch, the PHBV resin and the second PBAT resin to 1 (1.5-3) (2-3), and the pure PHBV resin material has high mechanical strength and modulus, but low elongation at break, and is a typical rigid material; the pure PBAT resin has high elongation at break and extremely low mechanical strength and modulus, and is a typical flexible material. According to the invention, PHB V resin and PBAT resin are compounded, and the rigidity and flexibility of the PHB V resin and the PBAT resin are combined, so that the composite material with higher mechanical strength, higher modulus and stronger flexibility is prepared. With the increase of the use amount of the PBAT resin, the mechanical strength and the modulus of the composite material are in a decreasing trend, and the elongation at break is in an increasing trend; with the increase of the PHBV resin dosage, the mechanical strength and the modulus of the composite material are in an ascending trend, and the elongation at break is in a descending trend. By balancing the ratio of PHB V resin to PBAT resin, a composite material having both excellent rigidity and excellent flexibility is prepared.
The tensile strength of the composite material is in a change trend of decreasing and increasing after increasing along with the increasing of the using amount of the PBAT resin, and is characterized in that the PHB V resin and the PBAT resin are subjected to phase separation phenomenon due to the problem of interfacial compatibility along with the increasing of the using amount of the PBAT resin, the interaction force between the two polymer materials is obviously lower than the interaction force in a single material, when the using amount of the PBAT is in the mass ratio range defined by the invention, the PBAT resin in the polymer matrix replaces the PHBV resin to occupy absolute dominance, the PBAT resin is converted from a disperse phase to a continuous phase, and the intermolecular force of the polymer of the composite material is increased, so that the tensile strength of the composite material is improved.
In some alternative examples, the barrel of the second twin-screw extruder is divided into 5 temperature zones with different temperature ranges along the material flow direction, namely a first zone, a second zone, a third zone, a fourth zone and a fifth zone in sequence.
In some alternative examples, the temperature of the first region is 140 to 155 ℃, for example 140 ℃, 141 ℃, 142 ℃, 143 ℃, 144 ℃, 145 ℃, 146 ℃, 147 ℃, 148 ℃, 149 ℃, 150 ℃, 151 ℃, 152 ℃, 153 ℃, 154 ℃, or 155 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In some alternative examples, the temperature of the second region is 160 to 170 ℃, such as 160 ℃, 161 ℃, 162 ℃, 163 ℃, 164 ℃, 165 ℃, 166 ℃, 167 ℃, 168 ℃, 169 ℃, or 170 ℃, but the second region is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In some alternative examples, the temperature of the third region is 170 to 180 ℃, such as 170 ℃, 171 ℃, 172 ℃, 173 ℃, 174 ℃, 175 ℃, 176 ℃, 177 ℃, 178 ℃, 179 ℃, or 180 ℃, but the third region is not limited to the recited values, and other non-recited values within the range are equally applicable.
In some alternative examples, the temperature of the fourth region is 175-185 ℃, such as 175 ℃, 176 ℃, 177 ℃, 178 ℃, 179 ℃, 180 ℃, 181 ℃, 182 ℃, 183 ℃, 184 ℃, or 185 ℃, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
In some alternative examples, the temperature of the fifth region is 180 to 190 ℃, for example, 180 ℃, 181 ℃, 182 ℃, 183 ℃, 184 ℃, 185 ℃, 186 ℃, 187 ℃, 188 ℃, 189 ℃, or 190 ℃, but the present invention is not limited to the recited values, and other non-recited values within the range are equally applicable.
In some alternative examples, the screw speed of the twin-screw extruder is 80-100 r/min, for example, 80r/min, 82r/min, 84r/min, 86r/min, 88r/min, 90r/min, 92r/min, 94r/min, 96r/min, 98r/min or 100r/min, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In a second aspect, the invention provides a bagasse fiber reinforced biodegradable composite material prepared by the preparation method in the first aspect.
Illustratively, the present invention provides a method for preparing a bagasse fiber-reinforced biodegradable composite material, the method comprising:
(1) Soaking bagasse in a modified solution composed of alkali and inorganic salt, wherein the mass fraction of the alkali in the modified solution is 1-5wt%, the mass fraction of the inorganic salt is 2-3wt%, the proportion of the bagasse to the modified solution is 1g (100-200) mL, mixing and stirring for 0.5-1.5 h, heating to 50-60 ℃ in a water bath, and then carrying out suction filtration to obtain modified bagasse, carrying out freeze drying and grinding crushing on the modified bagasse, wherein the freeze drying temperature is-60 to-30 ℃, and the freeze drying time is 5-6 h, so as to obtain modified bagasse powder with the fineness of 200-300 meshes; soaking the modified bagasse powder in a silane coupling agent solution with the weight percentage of 10-20%, wherein the ratio of the modified bagasse powder to the silane coupling agent solution is 1g (100-200) mL, the soaking time is 2-3 h, then carrying out suction filtration, washing and drying to obtain wet bagasse with the water content of 20-30 weight percent, the drying temperature is 70-80 ℃, the drying time is 1-2 h, and carrying out steam explosion on the wet bagasse to obtain modified bagasse fiber, the steam explosion pressure is 1-5 MPa, and the pressure maintaining time is 40-50 min;
(2) Dispersing montmorillonite in deionized water to form a montmorillonite suspension with the weight percent of 5-10wt%, and mixing the montmorillonite suspension with an iron salt solution with the weight percent of 0.1-0.5 mol/L to form a precursor solution, wherein the volume ratio of the montmorillonite suspension to the iron salt solution is 1 (1-2); dropwise adding alkali liquor into the precursor solution to adjust the pH value of the precursor solution to 10-11, stirring the precursor solution for 1-5 h and heating to 50-60 ℃ to obtain a reaction solution, standing and layering the reaction solution for 15-20 h to obtain a precipitate and a supernatant, washing and drying the precipitate at the drying temperature of 70-80 ℃ for 10-15 h to obtain inorganic modified montmorillonite;
(3) Dissolving cetyl trimethyl ammonium bromide and n-butyl alcohol in n-hexane, wherein the mass ratio of the cetyl trimethyl ammonium bromide to the n-butyl alcohol to the n-hexane is 1 (1-2) (8-9), mixing the mixture at the temperature of 4-6 ℃ for 20-30 min, adding the inorganic modified montmorillonite obtained in the step (2) and the calcium salt solution with the concentration of 1-5 mol/L, wherein the mass ratio of the cetyl trimethyl ammonium bromide to the inorganic modified montmorillonite to the calcium salt solution is 1 (0.5-0.7) (0.1-0.3), and uniformly mixing the inorganic modified montmorillonite and the calcium salt solution to form microemulsion; mixing 1-5 mol/L carbonate solution with the microemulsion, stirring for 10-20 min at the rotating speed of 700-800 r/min to obtain a reaction solution, standing and layering the reaction solution for 15-20 h to obtain a precipitate and a supernatant, washing, drying and grinding the precipitate, wherein the drying temperature is 70-80 ℃ and the drying time is 10-15 h to obtain the modified reinforcing filler;
(4) Mixing the modified bagasse fiber obtained in the step (1), the modified reinforcing filler obtained in the step (3) and the first PBAT resin according to the mass ratio of 1 (2-3) (5-6), stirring at the rotating speed of 800-1000 r/min for 30-40 min, injecting the mixture into a first double-screw extruder after uniformly mixing, setting the extrusion temperature to 160-170 ℃, setting the screw rotating speed to 100-200 r/min, and obtaining filler master batch after melt granulation; uniformly mixing filler master batch, PHBV resin and second PBAT resin according to the mass ratio of 1 (1.5-3) (2-3), injecting the mixture into a second double-screw extruder, setting the temperature of a first region to 140-155 ℃, setting the temperature of a second region to 160-170 ℃, setting the temperature of a third region to 170-180 ℃, setting the temperature of a fourth region to 175-185 ℃, setting the temperature of a fifth region to 180-190 ℃, setting the screw rotating speed to 80-100 r/min, and performing melt granulation to obtain the biodegradable composite material.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, PHB V resin is used as a matrix, PBAT resin is used as a toughening material, and modified bagasse fiber and modified reinforcing filler are used as reinforcing materials, so that the composite material which has excellent mechanical properties and can be completely biodegraded is prepared.
Polyadipic acid/butylene terephthalate (PBAT resin) is a synthetic polymer based on petrochemical resources, which is a fully biodegradable aliphatic-aromatic copolyester formed by esterification and polycondensation of 1, 4-butanediol with adipic acid and terephthalic acid. The PBAT resin is a random polymer, and can not form obvious crystallization, so that the PBAT resin has the physical characteristics of wide melting point and high flexibility (the elongation at break can reach more than 600 percent), belongs to an elastomer material with excellent ductility, and has lower mechanical strength.
PHBV resin is one of the most promising bioplastic in commercial application, has the advantages of high strength, good barrier property, high degradation rate and the like, but is brittle, poor in thermal stability and high in material cost, so that the wide application of the PHBV resin is limited; but the PBAT resin has good flexibility and thermal stability, but has lower mechanical strength and poorer gas barrier property. The PHBV resin and the PBAT resin have complementarity in material performance, and the composite material prepared by blending the PHBV resin and the PBAT resin has the advantages of both, can improve the defect of the PHBV resin while keeping the complete biodegradability, and improves the comprehensive performance of the composite material, but the production cost is still high. The bagasse is used as agricultural waste, has the advantages of abundant resources, low price, easy obtainment, low density, high specific strength and the like, is added into resin raw materials for melt blending and extrusion granulation, so that the biodegradable composite material is prepared, the bagasse can be used as a reinforcing material to improve the rigidity and crystallization performance of the composite material, the comprehensive utilization of bagasse resources can be realized, the added value of agricultural products is increased, the burden of shortage of wood resources is reduced, the production cost of the composite material is reduced, and the composite material meets the current social requirements and economic development, and has important significance for developing the composite material with high performance, low cost and environmental friendliness.
The untreated bagasse surface is covered with low molecular components such as pectin, lignin, hemicellulose and the like, so that the interfacial compatibility with a polymer matrix is poor, and the mechanical property of the finally prepared composite material is reduced; in order to solve the problem of poor compatibility of the bagasse fibers and the polymer matrix, the bagasse is chemically modified to reduce the surface polarity of the bagasse fibers, so that the mechanical reinforcing effect of the bagasse fibers can be better realized, and the comprehensive performance of the composite material is further improved. According to the invention, through the combined modification of alkali treatment, inorganic salt treatment and silane coupling agent treatment, the interface compatibility between the modified bagasse fiber and the polymer matrix is better, the modified bagasse fiber can be completely coated in the polymer matrix, the interface combination between the modified bagasse fiber and the polymer matrix is tighter, and the mechanical reinforcing effect of the bagasse fiber can be fully exerted.
The invention carries out the combined modification treatment of alkali and inorganic salt on bagasse, and the synergistic effect of the alkali and the inorganic salt is shown as follows: (1) The inorganic salt can enable lignin, hemicellulose, pectin, protein and other impurities on the surface of the bagasse to fall off from the surface of the bagasse, and the fallen lignin, hemicellulose, pectin, protein and other impurities are dissolved under the action of alkali; the direct dissolution of bagasse fibers caused by excessive alkali can be effectively avoided by a modification mode of firstly shedding and then dissolving. (2) Inorganic salt can permeate into a molecular chain lattice layer of the bagasse to destroy the wrapping structure of the bagasse, so that the bagasse fibers are completely exposed, and alkali can generate a chemical etching effect on the surfaces of the bagasse fibers along with the exposure of the bagasse fibers, so that the surface roughness of the bagasse fibers is improved, the interface contact area of the bagasse fibers and a polymer matrix is increased, and the mechanical meshing effect between the bagasse fibers and the polymer matrix is improved; meanwhile, the alkali can also react with hydroxyl groups on the surfaces of the bagasse fibers, so that the number of hydroxyl functional groups on the surfaces of the bagasse fibers is reduced, the surface polarity of the bagasse is reduced, the dispersion of the bagasse fibers in the polymer matrix is more uniform, the contact area between the bagasse fibers and the polymer matrix is increased, and further the interfacial effect and the bonding effect between the bagasse fibers and the polymer matrix are enhanced. However, as the degree of fibrillation of the bagasse after being soaked in alkali liquor is higher, the mechanical strength of the bagasse fiber is reduced due to high fibrillation, which is not beneficial to the improvement of the impact strength of the composite material.
The invention further adopts the silane coupling agent to modify on the basis of alkali treatment, so that the chemical bonding between bagasse fibers and a polymer matrix can be enhanced, and the silane coupling agent is a micromolecular surface modifier, so that the interfacial bonding strength between the bagasse fibers and the polymer matrix can be enhanced through the actions of chemical bonds and hydrogen bonds, thereby providing good interfacial affinity; in addition, the water solution of the silane coupling agent has extremely strong permeability and can permeate all gaps among the bagasse fibers, so that the whole surface of the bagasse fibers is further infiltrated, and the silane coupling agent and the surface of the bagasse fibers are kept in good infiltration contact; the silanol is formed after the alkoxy groups in the silane coupling agent are hydrolyzed, the silanol can perform a chemical bond action with hydroxyl groups in the bagasse fibers, and an organosilane molecular layer is formed on the surfaces of the bagasse fibers, so that the water absorbability of the bagasse fibers is reduced, the surface polarity of the bagasse fibers is reduced, the dispersibility of the bagasse fibers in a polymer matrix is obviously improved, the agglomeration of the bagasse fibers is effectively prevented, the defect number and the defect size at the interface of the bagasse fibers and the polymer matrix are reduced, and when the composite material is impacted, most of impact energy is consumed through good interface compatibility, so that the impact toughness of the finally prepared composite material is improved, and the impact strength of the composite material is improved. Therefore, the invention can effectively solve the problem of reduced impact strength caused by alkali treatment by modifying the silane coupling agent and utilizing the interface affinity effect of the silane coupling agent.
In order to improve the dispersibility of montmorillonite in a polymer matrix and improve the interfacial compatibility between the montmorillonite and the polymer matrix, the invention adopts ferric salt and CTAB to carry out inorganic modification and organic modification on the montmorillonite, and the modified montmorillonite can be uniformly adsorbed on the skeleton structure of the modified bagasse fiber in the melt extrusion process of the modified reinforcing filler and the modified bagasse fiber to form the skeleton supporting structure of the modified bagasse fiber/modified reinforcing filler, thereby greatly improving the impact strength of the composite material.
According to the invention, ferric salt is used as an inorganic modifier to carry out inorganic modification on montmorillonite, on one hand, iron ions in the ferric salt are replaced with cations on the surface of the montmorillonite, so that the interlayer spacing of the montmorillonite is increased; on the other hand, fe produced by oxidation reaction of iron salt under alkaline condition 3 O 4 Can be loaded between the montmorillonite layers to swell the montmorillonite, further increase the interlayer spacing, generate a large number of active surface adsorption sites and provide a basis for the subsequent adsorption of CTAB.
On the basis of inorganic modification, the invention organically modifies the montmorillonite by CTAB to hydrophobize the surface, after introducing CTAB into the montmorillonite layers, the interlayer spacing of the montmorillonite is increased, and the montmorillonite has good expansion performance, meanwhile, the interfacial polarity between the montmorillonite and the calcium carbonate particles is improved, a montmorillonite lamellar structure capable of containing larger calcium carbonate particles is formed, and sufficient active sites are provided for subsequent crystal grain nucleation of the calcium carbonate particles. In addition, the surface hydrophilicity of the montmorillonite which is not subjected to organic modification treatment is stronger, and the dispersion of the montmorillonite in PBAT resin melt is not facilitated. In addition, the stronger interaction between CTAB molecules and calcium carbonate particles can effectively prevent calcium carbonate crystals from growing, so that the particle size of the prepared calcium carbonate particles is smaller, and the montmorillonite and the calcium carbonate particles are protected by CTAB in a solution system and are in a stable state, so that the agglomeration is not caused, and the prepared montmorillonite/calcium carbonate modified reinforcing filler can be stably stored for a long time.
According to the invention, when the montmorillonite is modified, the modified reinforcing filler compounded by the modified montmorillonite and the calcium carbonate particles is prepared by a microemulsion method, the nucleation of calcium carbonate grains can be effectively promoted by virtue of active surface adsorption sites formed between montmorillonite layers after modification, meanwhile, the growth of the calcium carbonate grains can be effectively inhibited by utilizing a narrow area between montmorillonite layers, the growth of the calcium carbonate grains is inhibited by accelerating the nucleation of the calcium carbonate grains, and the nano-grade calcium carbonate particles can be obtained, wherein the particle size of the calcium carbonate particles can be controlled between a few nanometers and tens of nanometers.
Drawings
FIG. 1 is a flow chart of the preparation process of the biodegradable composite material provided in examples 1-15 of the present invention;
FIG. 2 is a photograph of biodegradable composite materials prepared in example 1, example 12 and example 13 of the present invention;
FIG. 3 is an XRD pattern of montmorillonite provided by the present invention and modified montmorillonite prepared in example 1 of the present invention;
FIG. 4 is an infrared spectrum of the montmorillonite provided by the present invention and the modified montmorillonite prepared in example 1 of the present invention;
FIG. 5 is a scanning electron microscope image of the modified montmorillonite prepared in example 1 of the present invention;
FIG. 6 is a cross-sectional Scanning Electron Microscope (SEM) image of the composite material prepared in example 1 and comparative example according to the present invention.
Detailed Description
The technical scheme of the invention is described in detail below with reference to specific embodiments and attached drawings. The examples described herein are specific embodiments of the present invention for illustrating the concept of the present invention; the description is intended to be illustrative and exemplary in nature and should not be construed as limiting the scope of the invention in its aspects. In addition to the embodiments described herein, other obvious solutions can be employed by those skilled in the art based on the disclosure of the present application, including those employing any obvious substitutions and modifications to the embodiments described herein.
Example 1
The embodiment provides a preparation method of a bagasse fiber reinforced biodegradable composite material, as shown in fig. 1, the preparation method comprises the following steps:
(1) Soaking bagasse in a modified solution consisting of sodium hydroxide and magnesium chloride, wherein the mass fraction of the sodium hydroxide in the modified solution is 1wt%, the mass fraction of the magnesium chloride is 3wt%, the proportion of the bagasse to the modified solution is 1 g/100 mL, mixing and stirring for 0.5h, heating to 60 ℃ in a water bath, then performing suction filtration to obtain modified bagasse, performing freeze drying and grinding crushing on the modified bagasse, wherein the freeze drying temperature is-60 ℃, and the freeze drying time is 5h, so as to obtain modified bagasse powder with the fineness of 200 meshes; soaking the modified bagasse powder in a 10wt% silane coupling agent KH550 solution, wherein the ratio of the modified bagasse powder to the silane coupling agent KH550 solution is 1g:200mL, the soaking time is 2h, then carrying out suction filtration, washing and drying to obtain wet bagasse with the water content of 20wt%, drying at 70 ℃ for 2h, and carrying out steam explosion on the wet bagasse to obtain modified bagasse fiber, wherein the steam explosion pressure is 1MPa, and the pressure maintaining time is 50min;
(2) Dispersing montmorillonite in deionized water to form a montmorillonite suspension with the weight percent of 5, and mixing the montmorillonite suspension with an iron salt solution with the mole ratio of 0.1mol/L to form a precursor solution, wherein the volume ratio of the montmorillonite suspension to the iron salt solution is 1:1; dropwise adding alkali liquor into the precursor solution to adjust the pH value of the precursor solution to 10, stirring the precursor solution for 1h and heating to 60 ℃ to obtain a reaction solution, standing and layering the reaction solution for 15h to obtain a precipitate and a supernatant, washing and drying the precipitate at a drying temperature of 70 ℃ for 15h to obtain inorganic modified montmorillonite;
(3) Dissolving cetyl trimethyl ammonium bromide and n-butyl alcohol in n-hexane, mixing the mixture at the temperature of 4 ℃ for 30min, and adding the inorganic modified montmorillonite obtained in the step (2) and the calcium chloride solution with the concentration of 1mol/L into the mixed solution, wherein the mass ratio of the cetyl trimethyl ammonium bromide to the inorganic modified montmorillonite to the calcium chloride solution is 1:0.5:0.1, and uniformly mixing to form a microemulsion; mixing 1mol/L sodium carbonate solution with the microemulsion, stirring for 20min at a rotating speed of 700r/min to obtain a reaction solution, standing and layering the reaction solution for 15h to obtain a precipitate and supernatant, washing, drying and grinding the precipitate, wherein the drying temperature is 70 ℃, and the drying time is 15h to obtain the modified reinforcing filler;
(4) Mixing the modified bagasse fiber obtained in the step (1), the modified reinforcing filler obtained in the step (3) and the first PBAT resin according to the mass ratio of 1:2:5, stirring at the rotating speed of 800r/min for 40min, injecting the mixture into a first double-screw extruder after uniform mixing, setting the extrusion temperature to 160 ℃, setting the screw rotating speed to 100r/min, and obtaining filler master batch after melting granulation; uniformly mixing filler master batch, PHBV resin and second PBAT resin according to the mass ratio of 1:1.5:2, then injecting the mixture into a second double-screw extruder, setting the temperature of a first region to 140 ℃, setting the temperature of a second region to 160 ℃, setting the temperature of a third region to 170 ℃, setting the temperature of a fourth region to 175 ℃, setting the temperature of a fifth region to 180 ℃, setting the screw speed to 80r/min, and carrying out melt granulation to obtain the biodegradable composite material.
XRD analysis was performed on the modified montmorillonite prepared in example 1, to obtain an XRD pattern shown in FIG. 3, and the characteristic diffraction peak of the modified montmorillonite was shifted to the left as compared with that of unmodified montmorillonite. The interlayer spacing of montmorillonite can be calculated by bragg formula 2dsin θ=λ, the interlayer spacing of unmodified montmorillonite is 1.21nm, and the interlayer spacing of modified montmorillonite is 1.27nm. This is because the iron ions are introduced into the montmorillonite after the modification of the montmorillonite by the iron salt, so that the metal cations in the montmorillonite are replaced, and the sheets of the montmorillonite are spread apart, so that the interlayer spacing is increased. In addition, the peaks of the modified montmorillonite at 2θ=30.1 °, 35.5 ° and 43.1 ° show (110), (200) and (211) crystal planes, respectively, which are attributed to Fe 3 O 4 Indicating Fe obtained by the reaction of ferric salt 3 O 4 Is successfully loaded between the montmorillonite layers in a dipping way.
The modified montmorillonite obtained in example 1 was subjected to infrared analysis to obtain an infrared spectrum as shown in FIG. 4, 991cm -1 The absorption peak at this point is the flexural vibration of the siloxane function. 1630cm -1 The absorption peak at the position corresponds to the water bending mode in the montmorillonite interlayer, and 1630cm of modified montmorillonite interlayer is modified -1 The intensity of the absorption peak at the position is obviously reduced, which indicates that the water between montmorillonite layers is gradually reduced in the modification process, and ferric salt enters the montmorillonite layers. Modified montmorillonite at 668cm -1 There appears a new absorption peak, ascribed to Fe-O functions of Fe3O4, which means Fe 3 O 4 Is successfully loaded between the montmorillonite layers.
Scanning electron microscope observation is carried out on the microscopic morphology of the modified montmorillonite prepared in the embodiment 1, so that an electron microscope photo shown in fig. 5 is obtained, and as can be seen from fig. 5, the layered structure of the modified montmorillonite is clear, and the inorganic modifier and the organic modifier fully enter the lamellar layers of the montmorillonite, so that the interlayer spacing is enlarged, and a uniform layered structure is formed; meanwhile, spherical Fe is attached to the surface of the modified montmorillonite 3 O 4 Particles, indicating Fe 3 O 4 Is successfully loaded to montmorilloniteIs a surface of the substrate.
Example 2
The embodiment provides a preparation method of a bagasse fiber reinforced biodegradable composite material, as shown in fig. 1, the preparation method comprises the following steps:
(1) Soaking bagasse in a modified solution consisting of sodium hydroxide and zinc chloride, wherein the mass fraction of the sodium hydroxide in the modified solution is 2wt%, the mass fraction of the zinc chloride is 2.8wt%, the proportion of the bagasse to the modified solution is 1g:120mL, mixing and stirring for 0.8h, heating to 58 ℃ in a water bath, performing suction filtration to obtain modified bagasse, performing freeze drying and grinding crushing on the modified bagasse, and performing freeze drying at the temperature of-50 ℃ for 5.2h to obtain modified bagasse powder with the fineness of 220 meshes; soaking the modified bagasse powder in a silane coupling agent KH550 solution with the weight percentage of 12%, wherein the ratio of the modified bagasse powder to the silane coupling agent KH550 solution is 1g to 180mL, the soaking time is 2.2h, then carrying out suction filtration, washing and drying to obtain wet bagasse with the water content of 22 weight percent, drying at the temperature of 72 ℃ for 1.8h, and carrying out steam explosion on the wet bagasse to obtain the wet bagasse, wherein the steam explosion pressure is 2MPa, and the pressure maintaining time is 48min;
(2) Dispersing montmorillonite in deionized water to form a montmorillonite suspension with the weight percent of 6, and mixing the montmorillonite suspension with a ferric salt solution with the mole ratio of 0.2mol/L to form a precursor solution, wherein the volume ratio of the montmorillonite suspension to the ferric salt solution is 1:1.2; dropwise adding alkali liquor into the precursor solution to adjust the pH value of the precursor solution to 10.2, stirring the precursor solution for 2 hours and heating to 58 ℃ to obtain a reaction solution, standing and layering the reaction solution for 16 hours to obtain a precipitate and a supernatant, washing and drying the precipitate at the drying temperature of 72 ℃ for 13 hours to obtain inorganic modified montmorillonite;
(3) Dissolving cetyl trimethyl ammonium bromide and n-butyl alcohol in n-hexane, mixing the mixture at 4.5 ℃ for 28min, adding the inorganic modified montmorillonite obtained in the step (2) and a calcium chloride solution with the concentration of 2mol/L, wherein the mass ratio of the cetyl trimethyl ammonium bromide to the inorganic modified montmorillonite to the calcium chloride solution is 1:0.55:0.15, and uniformly mixing to form a microemulsion; mixing 2mol/L sodium carbonate solution with the microemulsion, stirring for 18min at a rotating speed of 720r/min to obtain a reaction solution, standing and layering the reaction solution for 16h to obtain a precipitate and supernatant, washing, drying and grinding the precipitate, wherein the drying temperature is 72 ℃, and the drying time is 13h to obtain the modified reinforcing filler;
(4) Mixing the modified bagasse fiber obtained in the step (1), the modified reinforcing filler obtained in the step (3) and the first PBAT resin according to the mass ratio of 1:2.2:5.2, stirring for 38min at the rotating speed of 850r/min, injecting the mixture into a first double-screw extruder after uniform mixing, setting the extrusion temperature to 162 ℃, setting the screw rotating speed to 120r/min, and obtaining filler master batch after melt granulation; uniformly mixing filler master batch, PHBV resin and second PBAT resin according to the mass ratio of 1:1.8:2.2, injecting the mixture into a second double-screw extruder, setting the temperature of a first region to 145 ℃, setting the temperature of a second region to 162 ℃, setting the temperature of a third region to 172 ℃, setting the temperature of a fourth region to 178 ℃, setting the temperature of a fifth region to 182 ℃, setting the screw rotating speed to 85r/min, and carrying out melt granulation to obtain the biodegradable composite material.
Example 3
The embodiment provides a preparation method of a bagasse fiber reinforced biodegradable composite material, as shown in fig. 1, the preparation method comprises the following steps:
(1) Soaking bagasse in a modified solution consisting of sodium hydroxide and aluminum chloride, wherein the mass fraction of the sodium hydroxide in the modified solution is 3wt%, the mass fraction of the aluminum chloride is 2.5wt%, the proportion of the bagasse to the modified solution is 1g:150mL, mixing and stirring for 1h, heating to 55 ℃ in a water bath, and then carrying out suction filtration to obtain modified bagasse, carrying out freeze drying and grinding crushing on the modified bagasse, wherein the freeze drying temperature is-45 ℃, and the freeze drying time is 5.5h, so as to obtain modified bagasse powder with the fineness of 250 meshes; soaking the modified bagasse powder in 15wt% of silane coupling agent KH560 solution, wherein the ratio of the modified bagasse powder to the silane coupling agent KH560 solution is 1g:150mL, the soaking time is 2.5h, then carrying out suction filtration, washing and drying to obtain wet bagasse with the water content of 25wt%, drying at 75 ℃ for 1.5h, and carrying out steam explosion on the wet bagasse to obtain modified bagasse fiber, wherein the steam explosion pressure is 3MPa, and the pressure maintaining time is 45min;
(2) Dispersing montmorillonite in deionized water to form a montmorillonite suspension with the weight percent of 7, and mixing the montmorillonite suspension with a ferric salt solution with the mole ratio of 0.3mol/L to form a precursor solution, wherein the volume ratio of the montmorillonite suspension to the ferric salt solution is 1:1.5; dropwise adding alkali liquor into the precursor solution to adjust the pH value of the precursor solution to 10.5, stirring the precursor solution for 3 hours and heating to 55 ℃ to obtain a reaction solution, standing and layering the reaction solution for 17 hours to obtain a precipitate and a supernatant, washing and drying the precipitate, wherein the drying temperature is 75 ℃, and the drying time is 12 hours to obtain inorganic modified montmorillonite;
(3) Dissolving cetyl trimethyl ammonium bromide and n-butyl alcohol in n-hexane, mixing the mixture at 5 ℃ for 25min, adding the inorganic modified montmorillonite obtained in the step (2) and 3mol/L calcium chloride solution into the mixed solution, wherein the mass ratio of the cetyl trimethyl ammonium bromide to the inorganic modified montmorillonite to the calcium chloride solution is 1:0.6:0.2, and uniformly mixing to form microemulsion; mixing 3mol/L sodium carbonate solution with the microemulsion, stirring for 15min at a rotating speed of 750r/min to obtain a reaction solution, standing and layering the reaction solution for 17h to obtain a precipitate and supernatant, washing, drying and grinding the precipitate, wherein the drying temperature is 75 ℃, and the drying time is 12h to obtain the modified reinforcing filler;
(4) Mixing the modified bagasse fiber obtained in the step (1), the modified reinforcing filler obtained in the step (3) and the first PBAT resin according to the mass ratio of 1:2.5:5.5, stirring for 35min at the rotating speed of 900r/min, injecting the mixture into a first double-screw extruder after uniform mixing, setting the extrusion temperature to 165 ℃, setting the screw rotating speed to 150r/min, and obtaining filler master batch after melt granulation; uniformly mixing filler master batch, PHBV resin and second PBAT resin according to the mass ratio of 1:2:2.5, injecting the mixture into a second double-screw extruder, setting the temperature of a first region to 150 ℃, setting the temperature of a second region to 165 ℃, setting the temperature of a third region to 175 ℃, setting the temperature of a fourth region to 180 ℃, setting the temperature of a fifth region to 185 ℃, setting the screw speed to 90r/min, and carrying out melt granulation to obtain the biodegradable composite material.
Example 4
The embodiment provides a preparation method of a bagasse fiber reinforced biodegradable composite material, as shown in fig. 1, the preparation method comprises the following steps:
(1) Soaking bagasse in a modified solution consisting of potassium hydroxide and calcium chloride, wherein the mass fraction of the potassium hydroxide in the modified solution is 4wt%, the mass fraction of the calcium chloride is 2.2wt%, the proportion of the bagasse to the modified solution is 1 g/180 mL, mixing and stirring for 1.2h, heating to 52 ℃ in a water bath, and then performing suction filtration to obtain modified bagasse, and performing freeze drying and grinding crushing on the modified bagasse, wherein the freeze drying temperature is-40 ℃, and the freeze drying time is 5.8h, so as to obtain modified bagasse powder with the fineness of 280 meshes; soaking the modified bagasse powder in 18wt% of silane coupling agent KH570 solution, wherein the ratio of the modified bagasse powder to the silane coupling agent KH570 solution is 1g to 120mL, the soaking time is 2.8h, then carrying out suction filtration, washing and drying to obtain wet bagasse with the water content of 28wt%, drying at 78 ℃ for 1.2h, and carrying out steam explosion on the wet bagasse to obtain modified bagasse fiber, wherein the steam explosion pressure is 4MPa, and the pressure maintaining time is 42min;
(2) Dispersing montmorillonite in deionized water to form 8wt% montmorillonite suspension, and mixing the montmorillonite suspension with 0.4mol/L ferric salt solution to form a precursor solution, wherein the volume ratio of the montmorillonite suspension to the ferric salt solution is 1:1.8; dropwise adding alkali liquor into the precursor solution to adjust the pH value of the precursor solution to 10.8, stirring the precursor solution for 4 hours and heating to 52 ℃ to obtain a reaction solution, standing and layering the reaction solution for 18 hours to obtain a precipitate and a supernatant, washing and drying the precipitate at 78 ℃ for 11 hours to obtain inorganic modified montmorillonite;
(3) Dissolving cetyl trimethyl ammonium bromide and n-butyl alcohol in n-hexane, mixing the mixture at 5.5 ℃ for 22min, adding the inorganic modified montmorillonite obtained in the step (2) and the calcium chloride solution with the concentration of 4mol/L, wherein the mass ratio of the cetyl trimethyl ammonium bromide to the inorganic modified montmorillonite to the calcium chloride solution is 1:0.65:0.25, and uniformly mixing to form microemulsion; mixing 4mol/L sodium carbonate solution with the microemulsion, stirring at 780r/min for 12min to obtain a reaction solution, standing and layering the reaction solution for 18h to obtain a precipitate and supernatant, washing, drying and grinding the precipitate, wherein the drying temperature is 78 ℃ and the drying time is 11h to obtain the modified reinforcing filler;
(4) Mixing the modified bagasse fiber obtained in the step (1), the modified reinforcing filler obtained in the step (3) and the first PBAT resin according to the mass ratio of 1:2.8:5.8, stirring for 32min at the rotating speed of 950r/min, injecting the mixture into a first double-screw extruder after uniform mixing, setting the extrusion temperature to 168 ℃, setting the screw rotating speed to 180r/min, and obtaining filler master batch after melt granulation; uniformly mixing filler master batch, PHBV resin and second PBAT resin according to the mass ratio of 1:2.5:2.8, injecting the mixture into a second double-screw extruder, setting the temperature of a first region to 152 ℃, setting the temperature of a second region to 168 ℃, setting the temperature of a third region to 178 ℃, setting the temperature of a fourth region to 182 ℃, setting the temperature of a fifth region to 188 ℃, setting the screw speed to 95r/min, and performing melt granulation to obtain the biodegradable composite material.
Example 5
The embodiment provides a preparation method of a bagasse fiber reinforced biodegradable composite material, as shown in fig. 1, the preparation method comprises the following steps:
(1) Soaking bagasse in a modified solution consisting of potassium hydroxide and sodium chloride, wherein the mass fraction of the potassium hydroxide in the modified solution is 5wt%, the mass fraction of the sodium chloride is 2wt%, the proportion of the bagasse to the modified solution is 1 g/200 mL, mixing and stirring for 1.5h, heating to 50 ℃ in a water bath, then performing suction filtration to obtain modified bagasse, performing freeze drying and grinding crushing on the modified bagasse, wherein the freeze drying temperature is-30 ℃, and the freeze drying time is 6h, so as to obtain modified bagasse powder with the fineness of 300 meshes; soaking the modified bagasse powder in a 20wt% silane coupling agent KH570 solution, wherein the ratio of the modified bagasse powder to the silane coupling agent KH570 solution is 1g to 100mL, the soaking time is 3h, then carrying out suction filtration, washing and drying to obtain wet bagasse with the water content of 30wt%, the drying temperature is 80 ℃, the drying time is 1h, and carrying out steam explosion on the wet bagasse to obtain modified bagasse fiber, the steam explosion pressure is 5MPa, and the pressure maintaining time is 40min;
(2) Dispersing montmorillonite in deionized water to form a montmorillonite suspension with the weight percent of 10, and mixing the montmorillonite suspension with a ferric salt solution with the mole ratio of 0.5mol/L to form a precursor solution, wherein the volume ratio of the montmorillonite suspension to the ferric salt solution is 1:2; dropwise adding alkali liquor into the precursor solution to adjust the pH value of the precursor solution to 11, stirring the precursor solution for 5 hours and heating to 50 ℃ to obtain a reaction solution, standing and layering the reaction solution for 20 hours to obtain a precipitate and a supernatant, washing and drying the precipitate, wherein the drying temperature is 80 ℃, and the drying time is 10 hours to obtain inorganic modified montmorillonite;
(3) Dissolving cetyl trimethyl ammonium bromide and n-butyl alcohol in n-hexane, mixing the mixture at 6 ℃ for 20min, adding the inorganic modified montmorillonite obtained in the step (2) and 5mol/L calcium chloride solution into the mixed solution, wherein the mass ratio of the cetyl trimethyl ammonium bromide to the inorganic modified montmorillonite to the calcium chloride solution is 1:0.7:0.3, and uniformly mixing to form microemulsion; mixing 5mol/L sodium carbonate solution with the microemulsion, stirring for 10min at a rotating speed of 800r/min to obtain a reaction solution, standing and layering the reaction solution for 20h to obtain a precipitate and supernatant, washing, drying and grinding the precipitate, wherein the drying temperature is 80 ℃, and the drying time is 10h to obtain the modified reinforcing filler;
(4) Mixing the modified bagasse fiber obtained in the step (1), the modified reinforcing filler obtained in the step (3) and the first PBAT resin according to the mass ratio of 1:3:6, stirring at the rotating speed of 1000r/min for 30min, injecting the mixture into a first double-screw extruder after uniform mixing, setting the extrusion temperature to 170 ℃, setting the screw rotating speed to 200r/min, and obtaining filler master batch after melting granulation; uniformly mixing the filler master batch, PHBV resin and second PBAT resin according to the mass ratio of 1:3:3, injecting the mixture into a second double-screw extruder, setting the temperature of a first region to 155 ℃, setting the temperature of a second region to 170 ℃, setting the temperature of a third region to 180 ℃, setting the temperature of a fourth region to 185 ℃, setting the temperature of a fifth region to 190 ℃, setting the screw rotating speed to 100r/min, and carrying out melt granulation to obtain the biodegradable composite material.
Example 6
The present example provides a method for preparing a bagasse fiber reinforced biodegradable composite material, which is different from example 1 in that in step (1), the mass fraction of magnesium chloride in the modified solution is adjusted to 1.5wt%, and other process parameters and operation steps are identical to those in example 1.
Example 7
The present example provides a method for preparing a bagasse fiber reinforced biodegradable composite material, which is different from example 1 in that in step (1), the mass fraction of magnesium chloride in the modified solution is adjusted to 3.5wt%, and other process parameters and operation steps are identical to those of example 1.
Example 8
The present example provides a method for preparing a bagasse fiber reinforced biodegradable composite material, which is different from example 1 in that in step (1), the mixing and stirring time is 0.2h, and other process parameters and operation steps are exactly the same as example 1.
Example 9
The present example provides a method for preparing a bagasse fiber reinforced biodegradable composite material, which is different from example 1 in that in step (1), the mixing and stirring time is 1.8h, and other process parameters and operation steps are exactly the same as example 1.
Example 10
The present example provides a method for preparing a bagasse fiber reinforced biodegradable composite material, which is different from example 1 in that in step (1), the mass fraction of the alkylsilane coupling agent KH570 solution is adjusted to 2wt%, and other process parameters and operation steps are exactly the same as example 1.
Example 11
The present example provides a method for preparing a bagasse fiber reinforced biodegradable composite material, which is different from example 1 in that in step (1), the mass fraction of the alkylsilane coupling agent KH570 solution is adjusted to 10wt%, and other process parameters and operation steps are exactly the same as example 1.
Example 12
The present embodiment provides a method for preparing a bagasse fiber reinforced biodegradable composite material, which is different from embodiment 1 in that in step (4), the mass ratio of the modified bagasse fiber, the modified reinforcing filler and the first PBAT resin is adjusted to be 1:2:4, and other process parameters and operation steps are identical to those of embodiment 1.
Example 13
The present embodiment provides a method for preparing a bagasse fiber reinforced biodegradable composite material, which is different from embodiment 1 in that in step (4), the mass ratio of the modified bagasse fiber, the modified reinforcing filler and the first PBAT resin is adjusted to be 1:2:8, and other process parameters and operation steps are identical to those of embodiment 1.
Fig. 2 shows a sample physical photograph of the biodegradable composite materials prepared in examples 1, 12 and 13 according to the present invention, and it can be seen from fig. 2 that when the amount of the modified bagasse fiber added in example 13 is too low, the color of the sample is lighter, and when the amount of the biodegradable composite material added in example 12 is too high, the edge of the sample is in a region where fusion bonding is impossible.
Example 14
The present embodiment provides a method for preparing a bagasse fiber reinforced biodegradable composite material, which is different from embodiment 1 in that in step (4), the mass ratio of the filler masterbatch, the PHBV resin and the second PBAT resin is adjusted to be 1:1:2, and other process parameters and operation steps are identical to those of embodiment 1.
Example 15
The present embodiment provides a method for preparing a bagasse fiber reinforced biodegradable composite material, which is different from embodiment 1 in that in step (4), the mass ratio of the filler masterbatch, the PHBV resin and the second PBAT resin is adjusted to be 1:4:2, and other process parameters and operation steps are identical to those of embodiment 1.
Comparative example
This comparative example provides a process for the preparation of a bagasse fibre reinforced biodegradable composite material, differing from example 1 in that step (1) is omitted, bagasse is ground to a sugar cane powder, blended with a modified reinforcing filler and a first PBAT resin and melt granulated to obtain a filler masterbatch, and other process parameters and operating steps are exactly the same as in example 1.
Scanning electron microscopy observation was performed on the cross-sectional structures of the biodegradable composite materials prepared in example 1 and comparative example to obtain an electron micrograph as shown in fig. 6, and as can be seen from fig. 6, the cross-section of the composite material prepared using the unmodified bagasse has a large number of holes, the interface defect is serious, and it can be observed that the bagasse fibers are pulled out from the polymer matrix, and the existence of the holes is caused by pulling out the polymer matrix from the bagasse fibers on the one hand, and is caused by insufficient interfacial bonding force between the bagasse fibers and the polymer matrix on the other hand. The cross-sectional morphology of the composite material prepared by the modified bagasse fiber provided by the invention is greatly improved, defects such as holes and the like are basically not observed, and the pulling-out phenomenon of the bagasse fiber is obviously reduced.
The biodegradable composite materials prepared in examples 1 to 15 and comparative examples were tested for tensile strength, tensile modulus, flexural strength and flexural modulus as follows:
(1) Tensile Strength
Tensile mechanical property test reference ASTM D638-10, sample size reference dumbbell type II, sensor 10KN, test speed 5mm/min, 5 samples per example (comparative) were tested, and the average value was taken.
The tensile strength is calculated as follows:
in sigma 1 For tensile strength (MPa), F is the maximum load (N), b is the specimen width (mm), and h is the specimen thickness (mm).
(2) Tensile modulus
The tensile modulus was calculated as follows:
wherein E is 1 For tensile modulus (GPa), ΔF is the load delta (N) of the initial straight line segment on the load-displacement curve, ΔL is the gauge length L corresponding to the load delta ΔF 0 The deformation increment (mm) in the test piece is b, the test piece width (mm), and h is the test piece thickness (mm).
(3) Flexural Strength
Sample processing was equilibrated for 88h in a 50% constant temperature and humidity cabinet at 23℃with reference to ASTM D618-08 standard. Flexural mechanical testing with reference to standard ASTM D790-10, test piece size 160mm by 14mm by 8mm, sensor 2kN, test speed 17mm/min, 5 samples per example (comparative) were tested and averaged.
The bending strength is calculated as follows:
in sigma 2 For flexural strength (MPa), P is the maximum load (N), b is the specimen width (mm), h is the specimen thickness (mm), and l is the span (mm).
(4) Flexural modulus
The flexural modulus was calculated as follows:
wherein E is 2 Is the flexural modulus (GPa) and DeltaP is the load-deflection curveLoad increment (N) of the upper initial straight line segment, deltaS is deflection increment (mm) at the span center corresponding to DeltaP, b is test piece width (mm), and h is test piece thickness (mm).
The test results are shown in Table 1.
TABLE 1
| Tensile strength MPa | Tensile modulus GPa | Flexural Strength MPa | Flexural modulus GPa | |
| Example 1 | 13.5 | 1446 | 25.8 | 1865 |
| Example 2 | 14.3 | 1520 | 26.9 | 1904 |
| Example 3 | 15.8 | 1564 | 27.5 | 1920 |
| Example 4 | 17.6 | 1605 | 29.6 | 1955 |
| Example 5 | 16.2 | 1587 | 28.4 | 1933 |
| Example 6 | 8.1 | 1156 | 18.5 | 1458 |
| Example 7 | 10.3 | 1258 | 20.3 | 1540 |
| Example 8 | 9.6 | 1184 | 19.2 | 1484 |
| Example 9 | 13.8 | 1450 | 26.0 | 1868 |
| Example 10 | 7.5 | 1042 | 16.1 | 1385 |
| Example 11 | 9.4 | 1205 | 19.4 | 1496 |
| Example 12 | 7.3 | 1024 | 15.8 | 1377 |
| Example 13 | 11.7 | 1263 | 22.5 | 1684 |
| Example 14 | 6.3 | 941 | 15.2 | 1359 |
| Example 15 | 12.8 | 1365 | 24.6 | 1755 |
| Comparative example | 5.5 | 892 | 12.3 | 1240 |
From the test results provided in table 1, it can be seen that the biodegradable composite materials prepared in examples 1 to 5 have excellent comprehensive mechanical properties.
From the test results of example 1, example 6 and example 7, it can be seen that the mechanical properties of the finally prepared biodegradable composite material are affected by too low or too high mass fraction of the inorganic salt in the modified solution.
From the test results of example 1, example 8 and example 9, it can be seen that too short or too long a mixing and stirring time affects the mechanical properties of the finally prepared biodegradable composite material.
From the test results of example 1, example 10 and example 11, it can be seen that the mechanical properties of the finally prepared biodegradable composite material are affected by too low or too high mass fraction of the alkoxysilane coupling agent solution.
From the test results of example 1, example 12 and example 13, it can be seen that too low or too high an amount of modified bagasse fiber added affects the mechanical properties of the finally prepared biodegradable composite material.
As can be seen from the test results of example 1, example 14 and example 15, the mechanical properties of the finally prepared biodegradable composite material are affected by too low or too high addition amount of PHBV resin.
From the test results of example 1 and comparative example, it can be seen that the mechanical properties of the biodegradable composite material can be greatly improved by modifying bagasse.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (10)
1. A method for preparing a bagasse fiber reinforced biodegradable composite material, the method comprising:
soaking bagasse in a modified solution consisting of alkali and inorganic salt, mixing, stirring, heating in a water bath, performing suction filtration to obtain modified bagasse, and performing freeze drying and grinding and crushing on the modified bagasse to obtain modified bagasse powder; soaking the modified bagasse powder in a silane coupling agent solution, performing suction filtration, washing and drying to obtain wet bagasse, and performing steam explosion on the wet bagasse to obtain modified bagasse fibers;
dispersing montmorillonite in deionized water to form montmorillonite suspension, and mixing the montmorillonite suspension with ferric salt solution to form precursor solution; dropwise adding an alkali solution into the precursor solution to adjust the pH value of the precursor solution, stirring and heating the precursor solution to obtain a reaction solution, standing and layering the reaction solution to obtain a precipitate and a supernatant, and washing and drying the precipitate to obtain inorganic modified montmorillonite;
(III) dissolving cetyl trimethyl ammonium bromide and n-butanol in n-hexane, uniformly mixing, adding the inorganic modified montmorillonite and calcium salt solution obtained in the step (II) into the mixed solution, and uniformly mixing to form microemulsion; mixing and stirring carbonate solution and microemulsion to obtain a reaction solution, standing and layering the reaction solution to obtain a precipitate and supernatant, and washing, drying and grinding the precipitate to obtain a modified reinforcing filler;
Uniformly mixing the modified bagasse fiber obtained in the step (I), the modified reinforcing filler obtained in the step (III) and the first PBAT resin, then injecting the mixture into a first double-screw extruder, and obtaining filler master batch after melting and granulating; and uniformly mixing the filler master batch, PHBV resin and second PBAT resin, then injecting the mixture into a second double-screw extruder, and performing melt granulation to obtain the biodegradable composite material.
2. The preparation method of claim 1, wherein in the step (i), the mass fraction of the alkali in the modified solution is 1-5wt%;
the base comprises sodium hydroxide and/or potassium hydroxide;
the mass fraction of the inorganic salt in the modified solution is 2-3wt%;
the inorganic salt comprises any one or a combination of at least two of magnesium chloride, zinc chloride, aluminum chloride, calcium chloride or sodium chloride;
the proportion of the bagasse to the modifying solution is 1g (100-200 mL);
the mixing and stirring time is 0.5-1.5 h;
the temperature of the water bath heating is 50-60 ℃;
the temperature of freeze drying is minus 60 to minus 30 ℃;
the freeze drying time is 5-6 hours;
the fineness of the modified bagasse powder is 200-300 meshes.
3. The preparation method according to claim 1, wherein in the step (i), the mass fraction of the silane coupling agent solution is 5 to 8wt%;
The ratio of the modified bagasse powder to the silane coupling agent solution is 1g (100-200) mL;
the soaking time of the modified bagasse powder in the silane coupling agent solution is 2-3 hours;
the drying temperature is 70-80 ℃;
the drying time is 1-2 hours;
the moisture content of the dried wet bagasse is maintained to be 20-30wt%;
the steam explosion pressure adopted in the steam explosion process is 1-5 MPa;
the dwell time in the steam explosion process is 40-50 min.
4. The preparation method according to claim 1, wherein in the step (ii), the montmorillonite suspension has a mass fraction of 5-10wt%;
the concentration of the ferric salt solution is 0.1-0.5 mol/L;
the volume ratio of the montmorillonite suspension to the ferric salt solution is 1 (1-2);
the ferric salt in the ferric salt solution comprises any one or a combination of at least two of ferric chloride, ferric sulfate or ferric nitrate.
5. The method according to claim 1, wherein in the step (ii), alkali solution is added dropwise to the precursor solution to adjust the pH of the precursor solution to 10 to 11;
the stirring time of the precursor solution is 1-5 h;
the heating temperature of the precursor solution is 50-60 ℃;
The standing and layering time of the reaction liquid is 15-20 hours;
the drying temperature of the precipitate is 70-80 ℃;
and the drying time of the precipitate is 10-15 h.
6. The preparation method of claim 1, wherein in the step (III), the mass ratio of the hexadecyl trimethyl ammonium bromide to the n-butanol to the n-hexane is 1 (1-2): 8-9;
the mixing time of the cetyl trimethyl ammonium bromide, the n-butyl alcohol and the n-hexane is 20-30 min;
the mixing temperature of the cetyl trimethyl ammonium bromide, the n-butanol and the n-hexane is 4-6 ℃;
the mass ratio of the cetyl trimethyl ammonium bromide to the inorganic modified montmorillonite to the calcium salt solution is 1 (0.5-0.7): 0.1-0.3;
the concentration of the calcium salt solution is 1-5 mol/L.
7. The method according to claim 1, wherein in the step (iii), the concentration of the carbonate solution is 1 to 5mol/L;
the mixing and stirring time of the carbonate solution and the microemulsion is 10-20 min;
the rotational speed of mixing and stirring the carbonate solution and the microemulsion is 700-800 r/min;
the standing delamination time is 15-20 h;
the drying temperature is 70-80 ℃;
and the drying time is 10-15 h.
8. The preparation method of the modified bagasse fiber, according to claim 1, wherein in the step (IV), the mass ratio of the modified bagasse fiber to the modified reinforcing filler to the first PBAT resin is 1 (2-3): 5-6;
the mixing time of the modified bagasse fiber, the modified reinforcing filler and the first PBAT resin is 30-40 min;
the rotating speed of the mixing process of the modified bagasse fiber, the modified reinforcing filler and the first PBAT resin is 800-1000 r/min;
the extrusion temperature of the first double-screw extruder is 160-170 ℃;
the screw rotating speed of the first double-screw extruder is 100-200 r/min.
9. The preparation method of the composite material of the invention according to claim 1, wherein in the step (IV), the mass ratio of the filler master batch to the PHBV resin to the second PBAT resin is 1 (1.5-3): 2-3;
the inside of a charging barrel of the second double-screw extruder is divided into 5 temperature areas with different temperature ranges along the material flow direction, and the temperature areas are sequentially a first area, a second area, a third area, a fourth area and a fifth area;
the temperature of the first region is 140-155 ℃;
the temperature of the second area is 160-170 ℃;
the temperature of the third region is 170-180 ℃;
the temperature of the fourth region is 175-185 ℃;
the temperature of the fifth region is 180-190 ℃;
The screw rotating speed of the double-screw extruder is 80-100 r/min.
10. A bagasse fibre-reinforced biodegradable composite material prepared by the preparation method of any one of claims 1 to 9.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09137067A (en) * | 1995-11-15 | 1997-05-27 | Teijin Ltd | Biodegradable foam using bagasse as raw material and production thereof |
| CN1597769A (en) * | 2004-07-21 | 2005-03-23 | 华南理工大学 | Nano composite of polypyrrole/organic montmori and its preparation process and application |
| CN107793681A (en) * | 2016-08-30 | 2018-03-13 | 仲恺农业工程学院 | A kind of modified bagasse/plastic composite and preparation method and application |
| CN113234327A (en) * | 2021-05-22 | 2021-08-10 | 云南柒捌玖农业发展有限公司 | Method for producing degradable plastic from bagasse |
| CN114437524A (en) * | 2022-02-07 | 2022-05-06 | 天津科技大学 | Preparation method of sugarcane cellulose-based degradable composite material |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09137067A (en) * | 1995-11-15 | 1997-05-27 | Teijin Ltd | Biodegradable foam using bagasse as raw material and production thereof |
| CN1597769A (en) * | 2004-07-21 | 2005-03-23 | 华南理工大学 | Nano composite of polypyrrole/organic montmori and its preparation process and application |
| CN107793681A (en) * | 2016-08-30 | 2018-03-13 | 仲恺农业工程学院 | A kind of modified bagasse/plastic composite and preparation method and application |
| CN113234327A (en) * | 2021-05-22 | 2021-08-10 | 云南柒捌玖农业发展有限公司 | Method for producing degradable plastic from bagasse |
| CN114437524A (en) * | 2022-02-07 | 2022-05-06 | 天津科技大学 | Preparation method of sugarcane cellulose-based degradable composite material |
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