CN110724390A - Imitation biological matter pearl shell material and preparation method thereof - Google Patents
Imitation biological matter pearl shell material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing a biomass pearl shell material, which is characterized by comprising the following steps: s1: uniformly attaching the nano-substance to the biomass fiber by adopting a hot grinding method to prepare a nano-substance-biomass fiber composite material suspension; s2: adopting a freezing casting method to generate layered nacre-like structure matrix suspension from the suspension obtained in the step S1; s3: and (3) soaking the organic high polymer material into the matrix suspension obtained in the step S2, and then carrying out hot pressing to obtain the wooden pearl shell material. The preparation method is more environment-friendly, the prepared shell-like bionic layered material has higher mechanical strength and specific strength, and the functional group endows the material with new performance and has very wide application.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a biomimic pearl shell material and a preparation method thereof.
Background
In the course of long-term evolution, the natural world forms the biological material with perfect tissue structure form and unique excellent performance, such as gums and bones of mammals and shells of mollusks, especially the pearl shell layer in the shells has outstanding mechanical properties, and the shells of abalone are mainly made of CaCO3And a small amount of biological macromolecules, the hardness of which is ordinary CaCO 32 times of crystal, toughness is ordinary CaCO31000 times of crystal. The structures are mainly formed by utilizing a pre-organization body formed by self-assembly of organic macromolecules (protein, polysaccharide, lipid and the like) to manufacture a template and depositing molecular recognition inorganic molecules on the template. Inspired by nature, material researchers have attempted to reveal structural features and mechanisms of formation in biological systems for further application in material science design and fabrication.
The pearl oyster belongs to a natural organic/inorganic layered multilevel structure composite material, wherein 95 percent (volume fraction) of organic matrixes such as flaky aragonite and protein-polysaccharide organism are only about 5 percent, but the organic matrixes show extraordinary orderliness and strength on the nano level due to the regulation and control functions of the organic matrixes in the aspects of aragonite crystal nucleation, orientation, growth, space morphology and the like. The organic/inorganic layered structure of the pearl layer makes the structure beautiful and the mechanical property unique. Therefore, the method bionically prepares the multi-scale ordered inorganic or inorganic/organic hybrid material by an environment-friendly method, shows multiple functions of micro and macro, and becomes a research hotspot crossing multiple disciplines such as chemistry, material science, bioscience, nanotechnology and the like.
The defects of the fiber board, such as insufficient mechanical properties, moisture absorption and expansion, can cause the reduction of the dimensional stability of wood, easy bacterial erosion, easy organic matter pollution to lose beautiful color on the surface, serious surface deterioration after ultraviolet irradiation, inflammability under the conditions of high temperature or fire source and the like, thereby greatly limiting the application range and the field of the fiber board. Therefore, to solve these problems, an additional approach must be developed. With the development of the fiber board functional improvement technology, especially the artificial board is crossed and fused with the nano and bionic technology to prepare the high-added-value multifunctional composite novel structural material, which is one of the high and new technologies increasingly paid attention to in the field of fiber boards. The combination of the structure with high mechanical property of pearl shell and the fiber board improves the original defects of the fiber board, improves the performance of the fiber board and endows the fiber board with new special performance, so that the prepared material has double functions of fiber board characteristic and nano material characteristic, and is an important development direction for improving the fiber board functionality.
Disclosure of Invention
The invention aims to solve the technical problem of providing a bionic nacre and a preparation method thereof, wherein the preparation method is simple to operate, and greatly enriches the performance of the bionic material after the bionic material is generated.
On one hand, the invention provides a method for preparing a biomass pearl shell material, which comprises the following steps:
s1: uniformly attaching the nano-substance to the biomass fiber by adopting a hot grinding method to prepare a nano-substance-biomass fiber composite material suspension;
s2: adopting a freezing casting method to generate layered nacre-like structure matrix suspension from the suspension obtained in the step S1;
s3: and (3) soaking the organic high polymer material into the matrix suspension obtained in the step S2, and then carrying out hot pressing to obtain the wooden pearl shell material.
Further, the step S1 includes: crushing biomass fibers, and dissolving the biomass fibers and nano substances into distilled water together to form a suspension, wherein the biomass fibers: nano-material: the mass ratio of the distilled water is 1 (5 multiplied by 10)-40.2) 20; then sending the suspension into a colloid mill with the rotating speed of 2500-3000 rpm, and treating for 5-10 h to obtain the suspensionThen, sending the suspension into a disc grinder with the rotating speed of 2500-3000 rpm for treatment for 5-10 hours to obtain a nano substance-biomass fiber composite material suspension, wherein the particle size of the nano substance-biomass fiber composite material suspension is 50-500 nm; preferably, the mass ratio of the biomass fibers to the nano-substances to the distilled water is 1:0.02: 20; the rotating speed of the colloid mill and the disc mill is 2880rpm, and the processing time is 6 h;
further optionally, the nano-material in S1 is CaCO3、TiO2、ZnO、Ag、SiO2、Al2O3、Fe3O4、Mg(OH)2、Al(OH)3Any one or more of graphene, carbon fiber and carbon nano tube;
further optionally, the biomass fiber in S1 is any one or more of wood fiber, bamboo fiber, straw, wheat straw, corn stalk, cotton stalk, bagasse, reed, and awn stalk;
further, the step S2 includes: mixing the nano suspension obtained in S1 with 3.632g/L NaCl and 0.113g/LNa2SO4、0.332g/L NaHCO3、0.328g/L MgCl2·6H2O、0.284g/L CaCl2Uniformly mixing the mixed salt solution with 0.177g/L KCl, keeping the mixed salt solution at 40-60 ℃ for reacting for 36-60 hours to obtain mineralized nano biomass fiber suspension, pre-cooling the mineralized nano biomass fiber suspension to 1-5 ℃, then pouring the mineralized nano biomass fiber suspension into a mold, performing freeze casting at-196 to-30 ℃ in a liquid nitrogen environment, then putting the cast and molded sample into a freeze dryer, and performing freeze drying for 12-48 hours under 10-40 Pa to obtain a layered nacre-imitated structural matrix; preferably, the reaction temperature of the nanosuspension obtained in the S1 and the mixed salt solution is 50 ℃, and the reaction time is 48 hours; the pre-cooling temperature is 4 ℃; the freezing and casting temperature is-90 ℃, the freezing and casting mold material is polydimethylsiloxane, and the freezing and drying time is 24 hours;
further, the step S3 includes: dipping an organic high polymer material polymethyl methacrylate (PMMA), Polyethylene (PE), polyvinyl alcohol (PVA), p-phenylenediamine, thermoplastic polyurethane elastomer rubber, acrylic resin, polyetherimide or chitosan into the layered nacre-like structure matrix suspension obtained in S2, and then carrying out hot pressing for 0.5-24 h at 100-250 ℃ and under the pressure of 0.8-20 Mpa to obtain a finished product, wherein the mass percentage of the organic high polymer material in the finished product is 1-10%; preferably, the organic polymer material is polymethyl methacrylate (abbreviated as PMMA), polyethylene (abbreviated as PE) or polyvinyl alcohol; the hot pressing temperature is 168 ℃, the hot pressing pressure is 5MPa, and the hot pressing time is 1 h.
The invention also provides a bionic nacre material prepared by the preparation method.
Advantageous effects
1. The nano particles prepared by the method can be uniformly distributed on the fiber, are firmly attached, change the structure of the fiber, form a shell-like bionic layered material, have higher density under the same strength, and have wide application prospect in the field of production of the non-adhesive fiber board.
2. The method adopts the reaction of the biomass fiber, the inorganic nano material and the high molecular material, does not need to adopt polymerization reaction, and directly prepares the biomass fiber by mixing.
3. The method can incorporate, for example, CaCO3、TiO2And various functional groups of nano-scale particles such as ZnO and the like, thereby endowing the biomass material with various new functions, such as increasing various performances of photocatalysis, wear resistance, antibiosis, magnetism and the like of the material, and greatly expanding the application field of the composite material.
Drawings
FIG. 1 is CaCO obtained in example 33Scanning electron microscope image of wood fiber composite material
FIG. 2 is a scanning electron micrograph of a layered structure substrate of a pearl shell-like material obtained in example 3
FIG. 3 is a cross-sectional scanning electron micrograph of a pearl oyster obtained in example 3
FIG. 4 is the bending stress-strain curve of the nacre and other related wood materials obtained in example 3
FIG. 5 is a graph comparing the specific strength of the woody pearl oyster and other materials obtained in example 3, wherein 1. concrete; 2. glass; 3. a copper alloy; 4. natural anodonta woodiana shells; 5. synthesizing shells; 6. a polyurethane; al (7)2O3A polyacrylic acid composite; 8. an aluminum alloy; 9. polystyrene; 10. an epoxy resin; 11. quartz glass; 12. wooden pearl shell; 13. an iron alloy; 14. natural California red abalone shells; 15. a mussel shell; 16. natural nacre shell; 17. nylon; al (18)2O3 Material 19. silicon carbide material
FIG. 6 is a graph showing the degradation result of the wooden pearl shellfish material obtained in example 5 on formaldehyde
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby. It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which the invention pertains.
Example 1
A method for preparing a wooden pearl shell material comprises the following steps:
s1: pulverizing wood fiber, mixing with nano CaCO3Co-dissolved in distilled water to form a suspension, the wood fiber: nano-material: the mass ratio of the distilled water is 1: 5X 10-4: 20; then sending the suspension into a colloid mill with the rotation speed of 2500rpm, processing for 10 hours to obtain a suspension, and then sending the suspension into a disc grinder with the rotation speed of 2500rpm, and processing for 10 hours to obtain a nano substance-wood fiber composite material suspension, wherein the particle size of the nano substance-wood fiber composite material suspension is 50-500 nm; s2: mixing the nano suspension obtained in S1 with 3.632g/L NaCl and 0.113g/L Na2SO4、0.332g/LNaHCO3、0.328g/L MgCl2·6H2O、0.284g/L CaCl2Uniformly mixing the mixed salt solution with 0.177g/L KCl, keeping the mixed salt solution at 40 ℃ for reaction for 60 hours to obtain mineralized nano wood fiber suspension, precooling the mineralized nano wood fiber suspension to 1 ℃, then pouring the mineralized nano wood fiber suspension into a mold, performing freeze casting at-196 ℃ in a liquid nitrogen environment, then putting the cast and molded sample into a freeze dryer, and performing freeze drying at 40Pa, -30-20 ℃ for 24 hours to obtain a layered nacre-imitated structural matrix; s3: and (3) soaking an organic high polymer material PMMA into the layered nacre-like structure matrix suspension obtained in the step S2, and then carrying out hot pressing for 24 hours at the temperature of 100 ℃ and under the pressure of 0.8Mpa to obtain a finished product, wherein the mass percentage of the organic high polymer material in the finished product is 1%.
Example 2
A method for preparing a wooden pearl shell material comprises the following steps:
s1: pulverizing wood fiber, mixing with nano CaCO3Co-dissolved in distilled water to form a suspension, the wood fiber: nano-material: the mass ratio of the distilled water is 1:20: 20; then sending the suspension into a colloid mill with the rotating speed of 3000rpm, processing for 5 hours to obtain a suspension, and then sending the suspension into a disc grinder with the rotating speed of 3000rpm, and processing for 5 hours to obtain a nano substance-wood fiber composite material suspension, wherein the particle size of the nano substance-wood fiber composite material suspension is 50-500 nm; s2: mixing the nano suspension obtained in S1 with 3.632g/L NaCl and 0.113g/L Na2SO4、0.332g/L NaHCO3、0.328g/L MgCl2·6H2O、0.284g/L CaCl2Uniformly mixing the mixed salt solution with 0.177g/L KCl, keeping the mixed salt solution at 60 ℃ for 36 hours to obtain mineralized nano wood fiber suspension, pre-cooling the mineralized nano wood fiber suspension to 5 ℃, then pouring the mineralized nano wood fiber suspension into a mold, performing freeze casting at-30 ℃ in a liquid nitrogen environment, then putting the cast and molded sample into a freeze dryer, and performing freeze drying at 40Pa, -30-20 ℃ for 36 hours to obtain a layered nacre-like structure matrix; s3: soaking organic high molecular material PMMA in layered nacre-like structure matrix suspension obtained from S2, and heating at 250 deg.C and 20MpaPressing for 0.5h to obtain a finished product, wherein the mass percentage of the organic high polymer material in the finished product is 10%.
Example 3
A method for preparing a wooden pearl shell material comprises the following steps:
s1: pulverizing wood fiber, mixing with nano CaCO3Co-dissolved in distilled water to form a suspension, the wood fiber: nano-material: the mass ratio of the distilled water is 1:0.02: 20; then sending the suspension into a colloid mill with the rotating speed of 2880rpm, processing for 6 hours to obtain a suspension, and then sending the suspension into a disc grinder with the rotating speed of 2880rpm, and processing for 6 hours to obtain a nano substance-wood fiber composite material suspension, wherein the particle size of the nano substance-wood fiber composite material suspension is 50-500 nm; s2: mixing the nano suspension obtained in S1 with 3.632g/L NaCl and 0.113g/L Na2SO4、0.332g/LNaHCO3、0.328g/L MgCl2·6H2O、0.284g/L CaCl2Uniformly mixing the solution and a mixed salt solution consisting of 0.177g/L KCl, keeping the solution at 50 ℃ for reaction for 48 hours to obtain a mineralized nano wood fiber suspension, precooling the mineralized nano wood fiber suspension to 4 ℃, then pouring the mineralized nano wood fiber suspension into a mold, performing freeze casting at-90 ℃ in a liquid nitrogen environment, and freeze-drying a cast and molded sample for 36 hours at-30-20 ℃ under 20Pa in a freeze dryer; s3: and (3) soaking an organic high polymer material PMMA into the layered nacre-like structure matrix suspension obtained in the step S2, and then carrying out hot pressing for 1h at 168 ℃ and under the pressure of 5Mpa to obtain a finished product, wherein the mass percentage of the organic high polymer material in the finished product is 5%.
Example 4
A method for preparing a bamboo pearl shell material comprises the following steps:
s1: pulverizing bamboo fiber, mixing with nanometer SiO2Dissolving the bamboo fibers in distilled water together to form a suspension, wherein the ratio of the bamboo fibers: nano-material: the mass ratio of the distilled water is 1:0.02: 20; then sending the suspension into a colloid mill with the rotating speed of 2880rpm, processing for 6h to obtain the suspension, then sending the suspension into a disc grinder with the rotating speed of 2880rpm, processing for 6h to obtain the nano-materialThe particle size of the mixed suspension of the nano substance and the bamboo fiber composite material is 50-500 nm; s2: mixing the nano suspension obtained in S1 with 3.632g/L NaCl and 0.113g/L Na2SO4、0.332g/L NaHCO3、0.328g/LMgCl2·6H2O、0.284g/L CaCl2Uniformly mixing the mixture with a mixed salt solution consisting of 0.177g/L KCl, keeping the mixture at 50 ℃ for reaction for 48 hours to obtain a mineralized nano bamboo fiber suspension, precooling the mineralized nano bamboo fiber suspension to 4 ℃, then pouring the mineralized nano bamboo fiber suspension into a mold, performing freeze casting under the liquid nitrogen environment (-90 ℃), putting the cast and molded sample into a freeze dryer, and performing freeze drying for 36 hours under the vacuum condition of 20Pa, -30-20 ℃; s3: and (3) dipping the organic high polymer material PE into the layered nacre-like structure matrix suspension obtained in the step S2, and then carrying out hot pressing for 1h at 168 ℃ and under the pressure of 5Mpa to obtain a finished product, wherein the mass percentage of the organic high polymer material in the finished product is 5%.
Example 5
A method for preparing straw pearl shell material comprises the following steps:
s1: pulverizing straw fiber, mixing with nanometer TiO2Dissolving in distilled water to form a suspension, wherein the straw fiber: nano-material: the mass ratio of the distilled water is 1:0.02: 20; then sending the suspension into a colloid mill with the rotating speed of 2880rpm, processing for 6h to obtain a suspension, and then sending the suspension into a disc grinder with the rotating speed of 2880rpm, processing for 6h to obtain a nano substance-straw fiber composite material suspension, wherein the particle size of the nano substance-straw fiber composite material suspension is 50-500 nm; s2: mixing the nano suspension obtained in S1 with 3.632g/L NaCl and 0.113g/L Na2SO4、0.332g/LNaHCO3、0.328g/L MgCl2·6H2O、0.284g/L CaCl2Uniformly mixing with 0.177g/L KCl mixed salt solution, reacting at 50 deg.C for 48 hr to obtain mineralized nano straw fiber suspension, pre-cooling to 4 deg.C, pouring into a mold, performing freeze casting in liquid nitrogen environment (-120 deg.C), and freeze drying the cast sample in a freeze drierFreeze-drying for 36h under the conditions of 20Pa and minus 30-20 ℃; s3: and (3) soaking the organic high polymer material PVA into the layered nacre-like structure matrix suspension obtained in the step S2, and then carrying out hot pressing for 1h at 168 ℃ and under the pressure of 5Mpa to obtain a finished product, wherein the mass percentage of the organic high polymer material in the finished product is 5%.
Example 6
A method for preparing bagasse pearl shell material comprises the following steps:
s1: crushing bagasse fiber, and mixing with nano Fe3O4Co-dissolved in distilled water to form a suspension, the bagasse fibers: nano-material: the mass ratio of the distilled water is 1:0.02: 20; then sending the suspension into a colloid mill with the rotating speed of 2880rpm, processing for 6 hours to obtain a suspension, and then sending the suspension into a disc grinder with the rotating speed of 2880rpm, and processing for 6 hours to obtain a nano substance-bagasse fiber composite suspension, wherein the particle size of the nano substance-bagasse fiber composite suspension is 50-500 nm; s2: mixing the nano suspension obtained in S1 with 3.632g/L NaCl and 0.113g/L Na2SO4、0.332g/LNaHCO3、0.328g/L MgCl2·6H2O、0.284g/L CaCl2Uniformly mixing the mixture with a mixed salt solution consisting of 0.177g/L KCl, keeping the mixture at 50 ℃ for reaction for 48 hours to obtain a mineralized nano bagasse fiber suspension, precooling the mineralized nano bagasse fiber suspension to 4 ℃, then pouring the mineralized nano bagasse fiber suspension into a mold, performing freeze casting under the liquid nitrogen environment (-150 ℃), putting the cast and molded sample into a freeze dryer, and performing freeze drying for 36 hours under the vacuum condition of 20Pa, -30-20 ℃: and (3) soaking an organic high polymer material PMMA into the layered nacre-like structure matrix suspension obtained in the step S2, and then carrying out hot pressing for 1h at 168 ℃ and under the pressure of 5Mpa to obtain a finished product, wherein the mass percentage of the organic high polymer material in the finished product is 5%.
Experimental example 7: evaluation of wooden Pearl shellfish Material
1. The appearance characteristic is as follows:
FIG. 1 is CaCO obtained in example 33Scanning electron micrographs of the wood fiber composite: the figure reflects the passage of wood fibersIn the mechanical and chemical grinding stage, wood fibers are split, broken and refined at a nanometer scale; with CaCO3Compounding on the surface of the wood fiber through electrostatic adsorption and van der waals force;
FIG. 2 is a scanning electron micrograph of a layered structure substrate of a pearl shell-like material obtained in example 3; in the process of freezing and casting, the ice crystal induced assembly technology is adopted, and part of CaCO3The wood fiber composite is excluded from lamellar growing ice crystals and sandwiched between adjacent ice crystals to form a continuous network which is a structure determined by ice crystal templates. Finally, freeze drying is carried out, and an ordered layered structure is obtained after ice crystals are sublimated;
FIG. 3 is a cross-sectional scanning electron micrograph of a pearl oyster obtained in example 3; filling the freeze-dried ordered layered matrix with organic polymer soft matter to form hard CaCO3The/wood fiber composite material-soft organic polymer laminated structure can transfer and dissipate stress among layers in a stress process, so that stress concentration is avoided.
2. Performance testing
1) Bending strength: FIG. 4 is a comparison of bending stress strain curves of the woody pearl oyster obtained in example 3 and other related woody materials. The flexural strength reflects the ability of the panel to resist bending failure. In fig. 4, line a represents the bending stress strain curve of the pure wood fiberboard; b represents the bending stress strain curve of the wooden pearl oyster; c represents the bending stress strain curve of the disordered CaCO 3/wood fiber composite board. As can be seen from FIG. 4, the bending strength of the three composite materials is sequentially B (wooden pearl oyster) > C (disordered CaCO)3Wood fiber composite board > A (pure wood fiber board) the synergistic toughening effect of the wooden pearl oyster comes from organic polymer and two layers of CaCO3Interaction between wood fiber composites. If no organic polymer is present, CaCO3The/wood fibre composite layers are more prone to aggregation. CaCO3The anionic interaction between the two layers of the/wood fibre composite is relatively weak. Furthermore, CaCO3The wood fiber composite material has higher rigidity.
2) Specific strength: referring to the attached figure 5, the wood fiber raw component is low molecular weight C, H, O elements, and has lower density compared with other metal products and inorganic materials such as metal oxides, so the specific strength and specific toughness of the wood pearl shellfish material prepared by the method are higher than that of various alloys and composite materials thereof.
3) Functional groups are illustrated
To effectively explore the photocatalytic application of the wooden pearl shellfish material, we soaked the composite material (prepared from example 5) in strips (20mm × 7mm × 5mm) into an aqueous formaldehyde solution (0.15mmol/L) and then exposed to uv light. As shown in fig. 6, the formaldehyde degradation curve after the ultraviolet lamp irradiates for 360min shows that the formaldehyde is gradually degraded with the passage of the irradiation time, the change of the formaldehyde concentration is obviously reduced after 300min, and about 44.5% of formaldehyde is degraded in the wooden pearl shellfish material after 360 min. The result shows that the wooden pearl shellfish material can obviously degrade formaldehyde under the irradiation of ultraviolet light.
Unless specifically stated otherwise, the numerical values set forth in these examples do not limit the scope of the invention. In all examples shown and described herein, unless otherwise specified, any particular value should be construed as merely illustrative, and not restrictive, and thus other examples of example embodiments may have different values.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention, and they should be construed as being included in the following claims and description.
Claims (10)
1. The method for preparing the biomass pearl shell material is characterized by comprising the following steps:
s1: uniformly attaching the nano-substance to the biomass fiber by adopting a hot grinding method to prepare a nano-substance-biomass fiber composite material suspension;
s2: adopting a freezing casting method to generate layered nacre-like structure matrix suspension from the suspension obtained in the step S1;
s3: and (3) soaking the organic high polymer material into the matrix suspension obtained in the step S2, and then carrying out hot pressing to obtain the wooden pearl shell material.
2. The method for preparing biomass nacre material of claim 1, wherein the nano-material in step S1 is CaCO3、TiO2、ZnO、Ag、SiO2、Al2O3、Fe3O4、Mg(OH)2、Al(OH)3Any one or more of graphene, carbon fiber and carbon nano tube.
3. The method for preparing biomass pearl shell material according to claim 1, wherein the biomass fiber in S1 is any one or more of wood fiber, bamboo fiber, straw, wheat straw, corn stalk, cotton stalk, bagasse, reed and awn stalk.
4. The method for preparing biomass pearl shell material according to any one of claims 1 to 3, wherein the step S1 includes: crushing biomass fibers, and dissolving the biomass fibers and nano substances into distilled water together to form a suspension, wherein the biomass fibers: nano-material: the mass ratio of the distilled water is 1 (5 multiplied by 10)-40.2) 20; and then sending the suspension into a colloid mill with the rotating speed of 2500-3000 rpm, treating for 5-10 h to obtain a suspension, and then sending the suspension into a disc grinder with the rotating speed of 2500-3000 rpm, and treating for 5-10 h to obtain the nano substance-biomass fiber composite material suspension, wherein the particle size of the nano substance-biomass fiber composite material suspension is 50-500 nm.
5. The method for preparing biomass pearl shell material according to any one of claims 1 to 3The method of (a), wherein the step of S2 includes: mixing the nano suspension obtained in S1 with 3.632g/L NaCl and 0.113g/L Na2SO4、0.332g/LNaHCO3、0.328g/L MgCl2·6H2O、0.284g/L CaCl2Uniformly mixing the mixed salt solution with 0.177g/L KCl, keeping the mixed salt solution at 40-60 ℃ for reacting for 36-60 hours to obtain mineralized nano biomass fiber suspension, pre-cooling the mineralized nano biomass fiber suspension to 1-5 ℃, then pouring the mineralized nano biomass fiber suspension into a mold, performing freeze casting at-196 to-30 ℃ in a liquid nitrogen environment, then putting the cast and molded sample into a freeze dryer, and performing freeze drying at 10-40 Pa and-30-20 ℃ for 12-48 hours to obtain the layered nacre-imitated structural matrix.
6. The method for preparing biomass pearl shell material according to any one of claims 1 to 3, wherein the step S3 includes: any one of organic high polymer materials of polymethyl methacrylate, polyethylene, polyvinyl alcohol, p-phenylenediamine, thermoplastic polyurethane elastomer rubber, acrylic resin, polyetherimide or chitosan is dipped into the layered nacre-like structure matrix obtained in S2, and then hot pressing is carried out for 0.5-24 h at 100-250 ℃ and under the pressure of 0.8-20 Mpa, so as to obtain a finished product, wherein the mass percentage of the organic high polymer materials in the finished product is 1-10%.
7. The method for preparing biomass pearl shell material according to claim 4, wherein in step S1, the biomass fiber: nano-material: the mass ratio of the distilled water is 1:0.02: 20; the rotating speed of the colloid mill and the disc mill is 2880rpm, and the processing time is 6 h.
8. The method for preparing biomass pearl shell material according to claim 5, wherein in step S2, the reaction temperature of the nanosuspension and the mixed salt solution is 50 ℃ and the reaction time is 48 h; and the precooling temperature is 4 ℃; the freezing and casting temperature is-90 ℃, the freezing and casting mold material is polydimethylsiloxane, the pressure of freezing and drying is 20Pa, and the time is 24 h.
9. The method for preparing biomass pearl shell material according to claim 6, wherein in step S3, the organic polymer material is polymethyl methacrylate, polyethylene or polyvinyl alcohol; and the hot pressing temperature is 168 ℃, the hot pressing pressure is 5MPa, and the hot pressing time is 1 h.
10. A biomimetic pearl shell material prepared by the preparation method according to any one of claims 1 to 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574137A (en) * | 2020-04-29 | 2020-08-25 | 武汉理工大学 | Shell-like nacre layer material with layered structure and preparation method thereof |
| CN114230422A (en) * | 2022-01-11 | 2022-03-25 | 中国工程物理研究院化工材料研究所 | Pearl shell interface structure-imitated reinforced PBX compound and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105385875A (en) * | 2015-12-04 | 2016-03-09 | 中北大学 | Preparation method for shell-nacreous-layer-imitating magnesium-based composite material |
| JP2016094541A (en) * | 2014-11-14 | 2016-05-26 | 国立研究開発法人産業技術総合研究所 | Method for producing thermoplastic resin composition |
| CN107033493A (en) * | 2017-05-03 | 2017-08-11 | 马鞍山纽泽科技服务有限公司 | A kind of string environment friendly decoration board |
| CN108110133A (en) * | 2017-11-22 | 2018-06-01 | 浙江农林大学 | A kind of stratiform two-dimensional nano piece/carbonization fiber composite material and preparation method and application |
| CN108794932A (en) * | 2018-06-29 | 2018-11-13 | 钦州市宝业坭兴陶厂 | It a kind of method of modifying of nano-calcium carbonate and its applies in PVC wood plastic plank |
| EP3493221A1 (en) * | 2017-11-29 | 2019-06-05 | RISE Acreo AB | Method for manufacturing a conductive sheet |
| CN110126256A (en) * | 2019-05-24 | 2019-08-16 | 中南大学 | A kind of preparation method of bionical shellfish material |
-
2019
- 2019-10-18 CN CN201910994863.8A patent/CN110724390B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016094541A (en) * | 2014-11-14 | 2016-05-26 | 国立研究開発法人産業技術総合研究所 | Method for producing thermoplastic resin composition |
| CN105385875A (en) * | 2015-12-04 | 2016-03-09 | 中北大学 | Preparation method for shell-nacreous-layer-imitating magnesium-based composite material |
| CN107033493A (en) * | 2017-05-03 | 2017-08-11 | 马鞍山纽泽科技服务有限公司 | A kind of string environment friendly decoration board |
| CN108110133A (en) * | 2017-11-22 | 2018-06-01 | 浙江农林大学 | A kind of stratiform two-dimensional nano piece/carbonization fiber composite material and preparation method and application |
| EP3493221A1 (en) * | 2017-11-29 | 2019-06-05 | RISE Acreo AB | Method for manufacturing a conductive sheet |
| CN108794932A (en) * | 2018-06-29 | 2018-11-13 | 钦州市宝业坭兴陶厂 | It a kind of method of modifying of nano-calcium carbonate and its applies in PVC wood plastic plank |
| CN110126256A (en) * | 2019-05-24 | 2019-08-16 | 中南大学 | A kind of preparation method of bionical shellfish material |
Non-Patent Citations (4)
| Title |
|---|
| BARI, SARANG S. 等: "Biodegradable polymer nanocomposites: An overview", 《POLYMER REVIEWS》 * |
| QIAN TEMENG 等: "Fabrication and performance of wood fiber/carbon nanotube composite binderless fiberboard.", 《JOURNAL OF FORESTRY ENGINEERING》 * |
| WANG, JIN 等: "Layer-by-layer self-assembly of reduced graphene oxide on bamboo timber surface with improved decay resistance", 《EUROPEAN JOURNAL OF WOOD AND WOOD PRODUCTS》 * |
| 李坚 等: "大自然给予的启发——木材仿生科学刍议", 《中国工程科学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574137A (en) * | 2020-04-29 | 2020-08-25 | 武汉理工大学 | Shell-like nacre layer material with layered structure and preparation method thereof |
| CN111574137B (en) * | 2020-04-29 | 2021-04-23 | 武汉理工大学 | Shell-like nacre layer material with layered structure and preparation method thereof |
| CN114230422A (en) * | 2022-01-11 | 2022-03-25 | 中国工程物理研究院化工材料研究所 | Pearl shell interface structure-imitated reinforced PBX compound and preparation method thereof |
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