A composite layer

Abstract

The application discloses a composite material layer, which is Al a K b Ca c Mg d Si e C f O g The composite crystal composition is: a is 0.1-10, b is 0-5, c is 0-10, d is 0-10, e is 0-20, f is 0-95, and g is 5-90. The physical properties of the glass itself need to be improved, for example, the conductivity is weak, the resistance is high, and the strength is limited, and therefore how to strengthen the glass has important significance. The application discloses a composite material layer containing Al, K, Ca, Mg, Si, C and O, which can effectively improve the physical properties of the glass material, for example, the conductivity, the strength of the glass material and the elongation rate.

Description

Technical Field

[0001] This invention relates to a multilayer composite material, and more particularly to a composite material layer, belonging to the field of chemical materials. Background Technology

[0002] Glass is an inorganic non-metallic material primarily composed of silicon dioxide, containing trace elements. It exhibits excellent corrosion resistance and is stable to most acids, salts, and solvents (except concentrated alkalis and hydrofluoric acid). Currently, glass has various applications. For example, glass fibers, formed from drawn glass, can be used in automotive parts, high-speed rail and shipbuilding, and wind power. However, with the rapid development of the wind power industry, the recycling and disposal of large quantities of discarded wind turbine blades has become an urgent environmental problem. Glass powder can be used as a filler in coatings and other chemical products.

[0003] However, some physical properties of glass itself need to be improved, such as weak conductivity, high resistance, and limited strength. Therefore, how to strengthen glass is of great significance. Summary of the Invention

[0004] The present invention aims to solve at least one of the technical problems existing in the prior art.

[0005] Therefore, the present invention discloses a composite material layer, wherein the composite material layer is Al a K b Ca c Mg d Si e C f O g The composite crystal composition is as follows: a = 0.1-10, b = 0-5, c = 0-10, d = 0-10, e = 0-20, f = 0-95, and g = 5-90.

[0006] Furthermore, the method for preparing the composite material layer includes:

[0007] S1. A carbon source is placed on at least one side of a substrate and heated to a first temperature in an oxygen-free environment to form a first composite material layer on the surface of the substrate;

[0008] S2. Heating to a second temperature in an oxygen-containing environment until the first composite material layer is at least partially converted into a second composite material layer, wherein the carbon content of the second composite material layer is lower than that of the first composite material layer;

[0009] Wherein, at least one side of the substrate is a glass layer, and the carbon source is disposed on the glass layer.

[0010] Furthermore, the second composite material layer includes at least one intermediate layer, said intermediate layer being made of Al a1 K b1 Cac1 Mg d1 Si e1 O g1 The composite crystal composition is as follows: a1 is 0.5-5, b1 is 1-4, c1 is 0-8, d1 is 0-8, e1 is 0-15, and g1 is 70-90.

[0011] Furthermore, S1 specifically includes:

[0012] The carbon source and the substrate are mixed in a mass ratio of (0.5-3):(0.5-2.5) and heated in an oxygen-free environment to form a first composite material layer on the surface of the glass fiber, and then rapidly cooled.

[0013] Furthermore, the substrate may be selected from one or more of glass panels, glass fibers, and glass powder.

[0014] Furthermore, S2 specifically includes:

[0015] Heating in an oxygen-containing environment until the first composite material layer is at least partially converted into the second composite material layer, the second composite material layer being greater than 30 nm, followed by rapid cooling to obtain the composite material layer.

[0016] Furthermore, the oxygen-containing environment can be selected as an air atmosphere, which can be a closed environment or an air-flowing environment. When the air flows, the air flow rate is 50-200 ml / min.

[0017] Furthermore, the oxygen-free environment in S2 can be selected from one or more of nitrogen, helium, neon, argon, krypton, and xenon.

[0018] Furthermore, the first temperature is higher than the second temperature, and the difference between the first temperature and the second temperature does not exceed 300°C; the heating temperature of S1 is the softening temperature of the glass.

[0019] Furthermore, the carbon source is biomass, which is one or more of animal-derived biomass and plant-derived biomass.

[0020] Compared with the prior art, the present invention forms a composite material layer containing Al, K, Ca, Mg, Si, C and O, which can effectively improve the physical properties of glass materials, such as improving electrical conductivity, glass strength and reducing elongation. Attached Figure Description

[0021] Figure 1 This is a comparison diagram of the mechanical properties of glass fibers treated by co-pyrolysis and conventional pyrolysis according to an embodiment of the present invention;

[0022] Figure 2 Electron microscope images of embodiments of the present invention;

[0023] Figure 3 This is an EDS diagram of an embodiment of the present invention;

[0024] Figure 4 The image shows a comparison of the SEM microstructures of co-pyrolysis and conventional pyrolysis samples according to an embodiment of the present invention; the dense carbon layer and interface state formed by co-pyrolysis are shown.

[0025] Figure 5 This is a comparison of the XPS spectra of the co-pyrolysis sample according to an embodiment of the present invention and the sample of Comparative Example 1; wherein, the chemical state changes of K, Ca, Si, O and C elements are revealed;

[0026] Figure 6 This is a comparison diagram of the mechanical properties of glass fiber in Example 2 of the present invention and Comparative Example 2.

[0027] Figure 7 XRD test image of Embodiment 1 of the present invention

[0028] Figure 8 This is a SEM image of glass powder from an embodiment of the present invention;

[0029] Figure 9 This is a TEM image of a crystal on a dense crystal layer according to an embodiment of the present invention;

[0030] Figure 10 XRD pattern of an embodiment of the present invention;

[0031] Figure 11 These are TG-DSC images of the present invention before and after modification (Example 1);

[0032] Figure 12 These are resistance diagrams of the present invention before and after modification (Example 1). Detailed Implementation

[0033] To enable those skilled in the art to better understand the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments.

[0034] This invention discloses a composite material layer, wherein the composite material layer is Al. a K b Ca c Mg d Si e C f O g The composite crystal composition is as follows: a = 0.1-10, b = 0-5, c = 0-10, d = 0-10, e = 0-20, f = 0-95, and g = 5-90.

[0035] In some optional embodiments, the method for preparing the composite material layer includes:

[0036] S1. A carbon source is placed on at least one side of a substrate and heated to a first temperature in an oxygen-free environment to form a first composite material layer on the surface of the substrate;

[0037] S2. Heating to a second temperature in an oxygen-containing environment until the first composite material layer is at least partially converted into a second composite material layer, wherein the carbon content of the second composite material layer is lower than that of the first composite material layer;

[0038] Wherein, at least one side of the substrate is a glass layer, and the carbon source is disposed on the glass layer.

[0039] In some alternative embodiments, the second composite material layer includes at least an intermediate layer, said intermediate layer being made of Al a1 K b1 Ca c1 Mg d1 Si e1 O g1 The composite crystal composition is as follows: a1 is 0.5-5, b1 is 1-4, c1 is 0-8, d1 is 0-8, e1 is 0-15, and g1 is 70-90.

[0040] In some optional embodiments, S1 specifically includes:

[0041] The carbon source and the substrate are mixed in a mass ratio of (0.5-3):(0.5-2.5) and heated in an oxygen-free environment to form a first composite material layer on the surface of the glass fiber, and then rapidly cooled.

[0042] In some alternative embodiments, the substrate may be one or more of glass panels, glass fibers, and glass powder.

[0043] In some optional embodiments, the glass substrate is glass fiber.

[0044] In some optional embodiments, the glass fiber is waste glass fiber, which may be glass fiber from waste wind turbine blades.

[0045] In some optional embodiments, the diameter of the glass fiber monofilament is 15~20 μm.

[0046] In some optional embodiments, the glass fiber is recycled wind turbine blades. The recycled wind turbine blades are shredded material with a fragment area not exceeding 2 cm². 2 .

[0047] In some alternative embodiments, the waste wind turbine blades are specifically epoxy resin glass fiber composite materials.

[0048] In some optional embodiments, S2 specifically includes:

[0049] Heating in an oxygen-containing environment until the first composite material layer is at least partially converted into the second composite material layer, the second composite material layer being greater than 30 nm, followed by rapid cooling to obtain the composite material layer.

[0050] In some optional embodiments, the oxygen-containing environment may be an air atmosphere, which can be a closed environment or an air-flowing environment, wherein the air flow rate is 50-200 ml / min.

[0051] In some optional embodiments, the oxygen-free environment in S2 can be selected as one or more of nitrogen, helium, neon, argon, krypton, and xenon.

[0052] In some optional embodiments, the first temperature is higher than the second temperature, and the difference between the first temperature and the second temperature does not exceed 300°C; the heating temperature of S1 is the softening temperature of the glass.

[0053] The softening temperature of the glass is between 500-1200℃, and in this embodiment, it is preferably between 500-900℃.

[0054] In some optional embodiments, the carbon source is biomass, which is one or more of animal-derived biomass and plant-derived biomass.

[0055] In some optional embodiments, the carbon source is plant-derived biomass, which may be selected from herbaceous plant-derived biomass or woody plant-derived biomass. Herbaceous plant-derived biomass may include biomass such as corn cobs.

[0056] In some optional embodiments, the plant-derived biomass contains cellulose fibers, potassium, and calcium. Preferably, the potassium and calcium content in the plant-derived biomass is 2% or more. The cellulose fibers include at least one of lignin, cellulose, and hemicellulose.

[0057] Example 1

[0058] The collected corn cobs were rinsed with deionized water to remove surface impurities and dehydrated in an 80℃ forced-air drying oven for 12 hours. They were then crushed using a plant shredder, passed through a 20-mesh sieve, and stored in a sealed nitrogen atmosphere for later use. Waste fan blade fragments were crushed into 1-4cm uneven pieces and vacuum dried at 105℃ for 24 hours.

[0059] Corn cobs and glass fibers were mixed at a mass ratio of 1:1 and placed in a fixed-bed reactor. After nitrogen was introduced to purge the air, the temperature was raised to 600℃ and pyrolyzed at a constant temperature for 60 min under a nitrogen flow of 100 mL / min.

[0060] After the reactor was rapidly cooled to room temperature (5 min), the sample was taken out and ultrasonically cleaned with anhydrous ethanol to remove the loose carbon layer on the surface. Finally, it was dried at 80°C for 12 h under nitrogen protection to obtain the sample.

[0061] The atmosphere was then switched to air, the flow rate was 100 mL / min, and the temperature was raised to 550 °C and held for 30 min. The sample was then removed.

[0062] Example 2

[0063] The collected corn cobs were rinsed with deionized water to remove surface impurities and dehydrated in an 80℃ forced-air drying oven for 12 hours. After being crushed using a plant pulverizer, the cobs were passed through a 20-mesh sieve and stored in a sealed nitrogen environment for later use.

[0064] Corn cobs and alkali-free glass fibers were mixed at a mass ratio of 1:1 and placed in a fixed-bed reactor. After nitrogen was introduced to purge the air, the temperature was raised to 600℃ and pyrolyzed at a constant temperature for 60 min under a nitrogen flow of 100 mL / min.

[0065] After the reactor was rapidly cooled to room temperature (5 min), the sample was taken out and ultrasonically cleaned with anhydrous ethanol to remove the loose carbon layer on the surface. Finally, it was dried at 80°C for 12 h under nitrogen protection.

[0066] The atmosphere was then switched to air, the flow rate was 100 mL / min, and the temperature was raised to 550 °C and held for 30 min. The sample was then removed.

[0067] Example 3

[0068] The collected corn cobs were rinsed with deionized water to remove surface impurities and dehydrated in an 80℃ forced-air drying oven for 12 hours. After being crushed using a plant pulverizer, the cobs were passed through a 20-mesh sieve and stored in a sealed nitrogen environment for later use.

[0069] Corn cobs and alkali-free glass powder were mixed at a mass ratio of 1:1 and placed in a fixed-bed reactor. After nitrogen was introduced to purge the air, the temperature was raised to 600℃ and pyrolyzed at a constant temperature for 60 min under a nitrogen flow of 100 mL / min.

[0070] After the reactor was rapidly cooled to room temperature (5 min), the sample was taken out and ultrasonically cleaned with anhydrous ethanol to remove the loose carbon layer on the surface. Finally, it was dried at 80°C for 12 h under nitrogen protection.

[0071] The atmosphere was then switched to air, the flow rate was 100 mL / min, and the temperature was raised to 550 °C and held for 30 min. The sample was then removed.

[0072] Comparative Example 1

[0073] Waste wind turbine blade fragments: Waste wind turbine blade fragments were placed directly in a fixed bed and processed under the same conditions to obtain samples. The rest was the same as in Example 1.

[0074] Comparative Example 2 uses the glass fiber from Example 2.

[0075] Experimental tests were conducted on Examples 1 and 2, and Comparative Examples 1 and 2, and the results are as follows: Figure 1 As shown. Further analysis was conducted based on the experimental results of Example 1 and Comparative Example 1.

[0076] like Figure 1 As shown, the bar chart represents the tensile strength of a single fiber, the left axis represents the tensile strength scale, the line graph represents the elongation of a single glass fiber, and the right axis represents the elongation scale.

[0077] Specifically, the sample in Example 1 exhibited superior mechanical properties compared to Comparative Example 1, with a single fiber tensile strength of 1.00277 GPa, compared to 0.38716 GPa in Comparative Example 1, and similar to Comparative Example 2. The addition of corn cob significantly increased the tensile strength of the waste glass fiber by 2.59 times. The glass fiber elongation with the composite layer in Example 1 was 1.47%, while the elongation in Comparative Example 1 was 0.53%, with the addition of corn cob significantly increasing the elongation by 2.77 times. Furthermore, compared to the new glass fiber in Comparative Example 2, Example 2 also showed a significant improvement in single fiber tensile strength, by 1.36 times, indicating that the composite layer can effectively improve the tensile strength of glass fiber.

[0078] like Figure 2 As shown, (a) shows the layers after pyrolysis under nitrogen in Example 1, and (b) shows the distribution of each protective layer after pyrolysis under air in Example 1. It can be seen that after pyrolysis under nitrogen in Example 1, a crystalline silicate layer (second composite material layer), a crystalline carbon / silicate composite layer (third composite material layer), a crystalline carbon layer (first composite material layer), and an amorphous carbon layer (fourth material layer) are formed sequentially from the inside to the outside. After pyrolysis under air in Example 1, a crystalline silicate layer (second composite material layer), a crystalline carbon / silicate composite layer (third composite material layer), and a crystalline carbon layer (first composite material layer) are formed sequentially from the inside to the outside. For specific thicknesses, please refer to [reference needed]. Figure 2 content.

[0079] like Figure 3As shown, the elemental content of each layer in Example 1 was analyzed using EDS energy dispersive spectroscopy. Specifically, in Example 1 under nitrogen atmosphere, the carbon content of the first composite layer reached as high as 64.2 wt%, confirming the existence of a dense carbon layer after co-pyrolysis. During the air oxidation stage, Example 1 contained 3.32 wt% Ca and 4.9 wt% Mg, presumably (Mg,Ca,K)-Si-O mixed silicate formed by the reaction of K / Ca / Mg in biomass ash with SiO2. This interfacial phase can effectively inhibit oxidative erosion. The K element content was below the detection limit, suggesting that K may be enriched in the transition region of the carbon layer-fiber interface, exceeding the effective detection depth of EDS. This also indirectly indicates that a uniform protective layer covering K ions was formed on the surface of the co-pyrolyzed glass fiber after air oxidation.

[0080] like Figure 4 As shown, the appearance morphology of Example 1 and Comparative Example 1 was observed using a scanning electron microscope.

[0081] Specifically, during the air pyrolysis stage, a uniform and dense carbon layer was formed on the surface of Example 1, completely encapsulating the glass fiber, while Comparative Example 1 showed an exposed fiber surface and exhibited peeling.

[0082] The corn cob-waste wind turbine blade co-pyrolysis reinforced glass fiber prepared by this invention combines the synergistic advantages of biomass and composite materials. The obtained sample still maintains high tensile strength after oxidation treatment at 550℃, which is 2.59 times higher than that of the traditional pyrolysis method. The performance improvement is mainly due to the dual protection mechanism: (1) the graphitized carbon layer generated by corn cob pyrolysis provides a physical barrier; (2) the silicate interface phase enhances chemical stability. This is a unique effect that cannot be achieved by single pyrolysis.

[0083] like Figure 5 As shown, X-ray photoelectron spectroscopy was used to analyze the changes in chemical properties of Example 1N (glass fiber heated only in a nitrogen atmosphere), Example 1, Comparative Example 1N (glass fiber heated only in a nitrogen atmosphere), and Comparative Example 1.

[0084] Specifically, under nitrogen atmosphere, the sample of Example 1N exhibited significant interfacial chemical reconstruction characteristics: the C1s spectrum showed that the proportion of CC / CH bonds reached 62.41%, an increase of 12.36% compared to Comparative Example 1N, while the contents of OC=O bonds and C=O bonds decreased to 6.73% (a decrease of 9.72%) and 9.32% (a decrease of 4.56%), respectively, confirming that corn cob inhibits oxidation reaction and promotes graphitization of carbon layers; the O1s spectrum showed that the proportion of O-Si bonds was as high as 99%, an increase of 37.95% compared to Comparative Example 1N; the proportion of Si-O-Si bonds in the Si2p spectrum increased by 12.96%, and the bond energy was enhanced; the K2p plot showed that K only appeared in the co-thermal decomposition group, and no binding energy shift was found, but based on the increased proportion of O-Si in the O1s spectrum, it is speculated that K may catalyze the formation of Si-O-Si bonds. The Ca2p plot showed that the proportion of Ca2p3 / 2 decreased to 30%, indicating that Ca participates in the interfacial reaction. However, the peak position indicates that CaSiO3 was not formed, but it may exist in the form of amorphous Ca-Si-O.

[0085] After air oxidation, the C1s spectrum of Example 1A showed that the retention rate of CC / CH bonds increased by 7.3% compared with Comparative Example 1, and the O-Si bond dominated the interface composition, indicating that the biomass-derived dense carbon layer and silicate interface work together: on the one hand, oxygen penetration is blocked through the sp² hybrid carbon network, and on the other hand, the fiber surface structure is stabilized by silicate.

[0086] In addition, such as Figure 6 As shown, the product obtained after nitrogen pyrolysis in Example 2 has nearly twice the strength of the product obtained after air pyrolysis compared to Comparative Example 2. Although the elongation decreases, it only decreases from 3.5% of gf to 2.5%, forming a high-strength glass fiber. It can be seen that the composite structure formed by the crystalline silicate layer (second composite material layer), the crystalline carbon / silicate composite layer (third composite material layer), the crystalline carbon layer (first composite material layer), and the amorphous carbon layer (fourth material layer) can effectively improve the strength of the glass fiber. However, this structure has many additional carbon particles on its surface. Therefore, Example 2 of the present invention can be further subjected to air pyrolysis. By introducing air, the additional carbon particles are removed by heating, and the crystalline silicate layer (second composite material layer), the crystalline carbon / silicate composite layer (third composite material layer), and the crystalline carbon layer (first composite material layer) are formed sequentially from the inside to the outside. Under the action of the second composite material layer, the fiber strength of Example 2 is nearly 1.4 times higher than that of Comparative Example 2, and the elongation decreases from 3.55% of gf to 2.25%, still showing good strength improvement.

[0087] like Figure 7 As shown, the compositional analysis of each layer of the composite material layer on the surface of the glass fiber obtained in S1 and S2 in Example 1 was performed, and the results are as follows:

[0088]

[0089] As can be seen, the composite material layer in this embodiment of the invention is Al. a K b Ca c Mg d Si e C f O g The composite crystal composition is as follows: a = 0.1-10, b = 0-5, c = 0-10, d = 0-10, e = 0-20, f = 0-95, and g = 5-90.

[0090] Furthermore, the composite material layer consists of five layers of different compositions from the outside to the inside, with the innermost layer adhering to the glass surface of the substrate. Combined with the aforementioned tests, it can be determined that the composite material layer of the present invention can effectively improve the strength of glass fibers and improve the physical properties of glass.

[0091] like Figure 8 As shown, the modified glass powder surface exhibits a uniform dense crystalline layer, which can be further observed from... Figure 9 As can be seen in (a), it is a TEM image of a crystal in a dense crystal layer, and the lattice size of the crystal surface is 0.336 nm.

[0092] like Figure 10 As shown in the XRD pattern, the modified glass powder has obvious K characteristic peaks, indicating that the present invention can introduce K element into the surface of glass powder.

[0093] like Figure 11 As shown, the glass powder before modification and the glass powder after modification used in Example 3 were tested. The TG, DSC, and DTG curves all show that the modified glass powder exhibits less change with increasing heat compared to the unmodified glass powder, indicating that the modified glass powder has good antioxidant properties. Based on the aforementioned table, it is speculated that the composite material layer, due to its multiple layers containing carbon elements and various oxide structures, modifies the glass powder, thereby improving its antioxidant properties.

[0094] like Figure 12 As shown in the table, resistance tests were conducted on the glass powder before and after modification. It can be seen that the resistance of the modified glass powder decreased significantly, effectively improving its conductivity. Based on the aforementioned table, it is speculated that the composite material layers, due to the presence of carbon elements in multiple layers, modified the glass powder, thereby improving its conductivity.

[0095] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that after reading this application specification, they can still modify or make equivalent substitutions to the specific implementation of the present invention, but these modifications or changes do not depart from the protection scope of the pending claims of the present invention.

Claims

1. A composite material layer, characterized in that, The composite material layer is Al. a K b Ca c Mg d Si e C f O g The composite crystal composition is as follows: a = 0.1-10, b = 0-5, c = 0-10, d = 0-10, e = 0-20, f = 0-95, and g = 5-90.

2. The composite material layer according to claim 1, characterized in that, The method for preparing the composite material layer includes: S1. A carbon source is placed on at least one side of a substrate and heated to a first temperature in an oxygen-free environment to form a first composite material layer on the surface of the substrate; S2. Heating to a second temperature in an oxygen-containing environment until the first composite material layer is at least partially converted into a second composite material layer, wherein the carbon content of the second composite material layer is lower than that of the first composite material layer; Wherein, at least one side of the substrate is a glass layer, and the carbon source is disposed on the glass layer.

3. The composite material layer according to claim 1, characterized in that, The second composite material layer includes at least one intermediate layer, said intermediate layer being made of Al a1 K b1 Ca c1 Mg d1 Si e1 O g1 The composite crystal composition is as follows: a1 is 0.5-5, b1 is 1-4, c1 is 0-8, d1 is 0-8, e1 is 0-15, and g1 is 70-90.

4. The composite material layer according to claim 1, characterized in that, S1 specifically includes: The carbon source and the substrate are mixed in a mass ratio of (0.5-3):(0.5-2.5) and heated in an oxygen-free environment to form a first composite material layer on the surface of the glass fiber, and then rapidly cooled.

5. The composite material layer according to claim 2, characterized in that, The substrate may be one or more of glass panels, glass fibers, and glass powder.

6. The composite material layer according to claim 2, characterized in that, S2 specifically includes: Heating in an oxygen-containing environment until the first composite material layer is at least partially converted into the second composite material layer, the second composite material layer being greater than 30 nm, followed by rapid cooling to obtain the composite material layer.

7. The composite material layer according to claim 6, characterized in that, The oxygen-containing environment can be an air atmosphere, which can be a closed environment or an air-flowing environment. When the air flows, the air flow rate is 50-200 ml / min.

8. The composite material layer according to claim 2, characterized in that, The oxygen-free environment in S2 can be selected from one or more of nitrogen, helium, neon, argon, krypton, and xenon.

9. The composite material layer according to claim 2, characterized in that, The first temperature is higher than the second temperature, and the difference between the first temperature and the second temperature does not exceed 300°C; the heating temperature of S1 is the softening temperature of the glass.

10. A composite material layer according to claim 2, characterized in that, The carbon source is biomass, which is one or more of animal-derived biomass and plant-derived biomass.

Images