Enhanced fog droplet charging superomniphobic tube spray method and applications thereof

Abstract

The application discloses a kind of super double-tube spraying method and its application in biomass degradation, fungus growth, wrap deposition and the like.The super double-tube spraying method includes using high-pressure spray gun, and spraying mist drop after super double-tube, namely super double-tube spraying, wherein the super double-tube is PMMA polymer tube with super double-tube coating on inner wall, and the raw material for preparing the super double-tube coating includes TiO2 nanoparticle and hydrophobic epoxy resin.The application introduces super double-tube spraying technology, and by combining contact charging (CE) and induced charging (IE) effect, a kind of super double-tube spraying (SAP T-spraying) method is developed, which not only simplifies and optimizes the design of spraying, but also significantly improves the charge mass ratio (CMR) of mist drop, to realize efficient deposition on super-hydrophobic blade surface.

Description

Technical Field

[0001] This invention belongs to the field of electrostatic spraying technology, specifically relating to an ultra-dual-tube spraying method for enhancing droplet charge and its applications in biomass degradation, fungal growth, and envelopment deposition. Background Technology

[0002] Amidst global challenges to food security and ecological sustainability, the efficient use of pesticides and the optimization of biomass cycling have become critical scientific issues. In the field of pesticide application technology, electrostatic spraying technology, by improving the deposition efficiency of droplets on both the front and back of plant leaves, has become a promising method for reducing pesticide loss and achieving precise pesticide delivery. However, current electrostatic spraying technology faces challenges such as high cost and limited adaptability. In contrast, contact charging (gas-liquid contact, solid-liquid contact), as a common interfacial phenomenon, can generate a large amount of charge. Due to its material flexibility, simple system structure, and lack of external energy input, it has attracted increasing attention.

[0003] In the efficient conversion of lignocellulose biomass, traditional chemical treatment methods, such as catalysis, suffer from environmental hazards or economic infeasibility, while microbial methods are characterized by low efficiency and low yield. Therefore, developing environmentally friendly, economical, and efficient technologies is crucial for transforming these wastes into high-value products and achieving a closed agricultural cycle. Summary of the Invention

[0004] This invention introduces super-dual-tube spraying technology. By combining contact charging (CE) and induced charging (IE) effects, a super-dual-tube spraying (SAP T-spaying) method is developed, which simplifies and optimizes spray design and significantly improves the charge-to-mass ratio (CMR) of droplets, achieving efficient deposition on superhydrophobic blade surfaces.

[0005] In a first aspect, the present invention provides a superhydrophobic tube spraying method (SAP T-spraying), comprising using a spray bottle or a high-pressure spray gun to spray droplets through the superhydrophobic inner wall of a superhydrophobic tube, i.e., superhydrophobic tube spraying, wherein the superhydrophobic tube is a PMMA polymer tube with a superhydrophobic coating on its inner wall, and the raw materials for preparing the superhydrophobic coating include TiO2 nanoparticles and hydrophobic epoxy resin.

[0006] In some embodiments, the preparation method of the superhydrophobic (SAP) tube includes: uniformly dispersing hydrophobic TiO2 nanoparticles in ethyl acetate, then adding hydrophobic epoxy resin at a mass ratio of 1:10 under magnetic stirring, and continuously stirring for 10 min to obtain a solution; The solution was then sprayed onto the inner wall of the PMMA polymer tube using a spray gun. After curing at room temperature for 24 hours, a robust superhydrophobic coating was formed, resulting in a superhydrophobic (SAP) tube.

[0007] In some embodiments, the preparation method of the superhydrophobic (SAP) tube involves spraying a gun at a pressure of 0.1-0.2 MPa, a distance of 20-30 cm between the nozzle and the tube opening, spraying for about 5 seconds at each of the two tube openings, and ensuring that the coating is applied evenly and remains crack-free after drying.

[0008] Super-dual-channel spraying (SAP T-spraying) significantly enhances the positive charge of droplets through complex dynamic behaviors of anti-wind bouncing and wall-attached vortices. The charging effect increases with increasing spray pressure, with a maximum charge-to-mass ratio reaching 1845.11 nC·g. -1 It has the effect of improving the efficiency of encirclement deposition.

[0009] In a second aspect, the present invention provides the application of the super dual-channel spray method in improving encirclement deposition efficiency.

[0010] In some embodiments, the application includes: using a high-pressure spray gun to spray a spray solution onto the crop through an ultra-diffuse nozzle, the spray solution being selected from at least one of water-soluble 2,4-epibrassinolide, pyraclostrobin suspension, sodium nitrophenolate aqueous solution, and amino acid-containing water-soluble fertilizer.

[0011] SAP T-spraying technology effectively and stably improves the positive charge properties of low surface tension agricultural additives (such as didodecyl dimethyl ammonium bromide, DOAB), exhibiting superior deposition performance and more stable deposition effects in droplet envelopment deposition applications. Water-based sprays containing four pesticide formulations—water-soluble 2,4-epibrassinolide (0.01%), pyraclostrobin suspension (30%), sodium nitrophenolate aqueous solution (1.8%), and an amino acid-containing water-soluble fertilizer—achieved deposition efficiencies of 4.01, 2.69, 1.68, 1.85, and 4.11 d mm on superhydrophobic leaves, respectively. -2 This far exceeds the level of electrostatic sprayers (≥ 1 d mm). -2 ).

[0012] In a third aspect, the present invention provides the application of the super dual-channel spray method in biomass degradation.

[0013] In some embodiments, the application includes collecting droplets sprayed by the super-dual-channel spray method to process biomass feedstocks to degrade the biomass therein.

[0014] The biomass raw materials include at least one of cottonseed hulls, wheat bran, and corn cobs.

[0015] The biomass includes at least one of lignin, cellulose, and hemicellulose.

[0016] In a fourth aspect, the present invention provides the application of the super-dual-channel spray method in promoting fungal growth.

[0017] In some embodiments, the application includes spraying water onto the surface of the substrate using the super-dual-channel spray method, followed by normal cultivation.

[0018] In the efficient conversion of lignocellulose biomass, nature provides insights into the recycling of complex organic matter, as evidenced by the abundant mushroom growth following thunderstorms. This effect can be attributed to the generation of charged droplets and reactive oxygen species (ROS) by atmospheric discharge, which significantly stimulate fungal growth. The droplets generated by the SAP T-spraying of this invention produce charged droplets and ROS, which can efficiently degrade recalcitrant lignocellulose and promote the proliferation of beneficial fungi. These fungi recycle nutrients into the Earth's ecosystem through decay and carbon sequestration, forming a mutually reinforcing cycle between substrate decomposition and microbial growth, moving towards targeted bio-promotion. This invention not only innovatively reveals a kinetic mechanism for the generation of charged droplets but also establishes a functional model that effectively combines lignocellulose degradation with microbial recycling, providing a practical pathway for achieving circular agriculture.

[0019] Superoxide radicals (SOPs) during ultra-dual-channel spraying process . O2 - The presence of superoxide radicals: When droplets collide with the pipe wall, electrocatalysis induces the generation of superoxide radicals. Highly charged droplets rich in reactive oxygen species enable the super-dual-channel spray to promote the degradation of lignocellulose and the growth of edible fungi. In practical agricultural applications promoting the growth of edible fungi, SAP T-spraying has been found to alter the fungal community structure and species diversity, thereby accelerating the degradation of lignocellulose components in cottonseed hulls, wheat bran, and corn cobs, and promoting the germination and reproduction of edible fungi. Regarding the mechanism of SAP T-Spraying in degrading lignocellulose, on the one hand, the SAP T-Spraying water... . O2 - SAP T-spraying can oxidize refractory lignocellulose, making it more susceptible to enzymatic attack and degradation. Conversely, highly charged droplets may alter the electrostatic environment surrounding the degrading enzymes, promoting lignocellulose degradation by inducing changes in their binding affinity to the substrate or catalyzing conformational changes in the α-helical structure. SAP T-spraying forms a bidirectional feedback loop in promoting lignocellulose degradation and stimulating the proliferation of lignocellulose-degrading fungi, demonstrating its significant potential in the utilization of agricultural waste and the conversion of high-value products. It provides a powerful and scalable technological approach to promoting sustainable agriculture. Attached Figure Description

[0020] Figure 1 The paper presents a comparative analysis of the degradation of lignin, cellulose, and hemicellulose in cottonseed hulls (a), wheat bran (b), and corn cobs (c) substrates in Example 2 of the present invention under D-spraying and SAP T-spraying treatments.

[0021] Figure 2 The results of promoting the growth of edible fungi by SAP T-spraying and D-spraying treatments in Example 3 of the present invention are shown.

[0022] Figure 3 The results of enhanced encirclement deposition after SAP T-spraying, D-spraying, and SHB T-spraying treatments in Example 4 of the present invention are shown. Detailed Implementation

[0023] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. The following embodiments are for illustrative purposes only and should not be considered as limiting the scope of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without inventive effort are within the scope of protection of this invention.

[0024] Example 1 Preparation of superhydrophobic (SAP) tubes: TF-100 superhydrophobic coating (Chengdu Gaojie Technology Co., Ltd.) is used, which consists of two parts: a main agent and an auxiliary agent. The main agent is hydrophobic TiO2 nanoparticles, which serve as the functional component; the auxiliary agent is hydrophobic epoxy resin, which serves as the binding matrix.

[0025] The preparation process includes the following optimized steps: Hydrophobic TiO2 nanoparticles are uniformly dispersed in ethyl acetate, followed by the addition of a curing agent, hydrophobic epoxy resin, at a ratio of main agent to auxiliary agent of 1:10 (m / m) under magnetic stirring. The mixture is stirred continuously for 10 minutes to obtain a homogeneous solution. The solution is then uniformly sprayed onto the inner wall of a PMMA polymer tube (10cm long, 18mm inner diameter, 22mm outer diameter) using a spray gun. After heat curing at room temperature for 24 hours, a robust superhydrophobic coating is formed, resulting in a superhydrophobic (SAP) tube. The spray gun pressure is 0.1-0.2 MPa, the nozzle-to-tube distance is 20-30 cm, and the spraying time is approximately 5 seconds for each of the two tube openings. The coating is uniformly applied and shows no cracks after drying.

[0026] Superhydrophobic T-spraying (SAP T-spraying) Formation: This experiment used two spraying devices, including a 300ml spray bottle and a high-pressure spray gun. The high-pressure spray gun consists of a pressure spray gun with a metal nozzle connected to a pressure pump. This spray gun delivers an aqueous solution through a polymer tube with a superhydrophobic (SAP) coating on its inner wall. During spraying, the nozzle is aimed at the PMMA polymer tube with the superhydrophobic coating on its inner wall; the droplets ejected after passing through the superhydrophobic tube constitute the superhydrophobic T-spray.

[0027] The charge-to-mass ratio (CMR) of the spray was determined using an electrometer (Keithley 6517B). During spraying, the nozzle was maintained at a fixed distance of 30 cm from the aluminum foil of the metal receiver, and the spraying time was 1 s. To ensure the accuracy and repeatability of the measurements, each measurement was repeated three times, and the data are presented as averages. All measurements were performed under controlled environmental conditions: temperature 25 ± 1 °C, relative humidity 45 ± 2%. The spray gun was connected to an air pump; the CMR varied under different pump pressures, increasing with increasing spray pressure. The highest CMR reached 1845.11 nC·g. -1 It has the effect of improving the efficiency of encirclement deposition.

[0028] Example 2 This embodiment selects common biomass materials such as cottonseed hulls, wheat bran, and corn cobs to compare the effects of tubular spraying on the degradation of lignocellulose.

[0029] Experimental Methods: Droplets generated by a super-dual-tube spray technique (50 ml) were collected and used to soak cottonseed hulls (5.0 g), wheat bran (3.0 g), and corn cob (3.0 g) in petri dishes. After one week, the decomposed samples were collected, washed, and dried. The lignocellulose composition of the substrate samples was then determined using the NREL method. The spray nozzle pressure was controlled at 0 kV before spraying, and the experimental environment was controlled at a temperature of 25 ± 1 °C and a relative humidity of 45 ± 2%. (SAP T-spraying) Using the same volume of deionized water as a control (D-spraying), immersion was performed under the same experimental conditions, and the results are as follows. Figure 1 As shown.

[0030] Quantitative results showed that the lignocellulose content of cottonseed hulls, wheat bran, and corn cobs treated with super dual-spraying (SAP T-spraying) was significantly lower than that of samples treated with direct deionized water soaking (D-spraying), indicating that SAP T-spraying has a better conversion and utilization rate for lignocellulose.

[0031] On the seventh day, inside the cottonseed hull ( Figure 1a) The contents of lignin, cellulose, and hemicellulose were 29.08%, 16.69%, and 16.77%, respectively. Compared with the D-spraying treatment (34.32%, 21.84%, and 18.59%), the degradation rates of lignin, cellulose, and hemicellulose increased by 5.24%, 5.15%, and 1.82%, respectively. Wheat bran ( Figure 1 b) After internal SAP T-spraying treatment, the contents of lignin, cellulose, and hemicellulose were 6.76%, 7.87%, and 12.88%, respectively. Compared with D-spraying treatment (8.07%, 11.85%, and 18.24%), the degradation rates of lignin, cellulose, and hemicellulose increased by 4.85%, 0.76%, and 3.21%, respectively. Corn cob ( Figure 1 c) After internal SAP T-spraying treatment, the contents of lignin, cellulose and hemicellulose were 14.4%, 23.70% and 18.46%, respectively. Compared with D-spraying treatment (19.25%, 24.46% and 21.67%), the degradation rates of lignin, cellulose and hemicellulose increased by 4.85%, 0.76% and 3.21%, respectively.

[0032] These data clearly demonstrate that SAP T-spraying accelerates the degradation of lignocellulose components in each substrate.

[0033] Example 3 Water was sprayed onto the surface of the substrate using a super-dual-pipe spraying technique (SAP T-spraying), while the control group was directly sprayed using a spray bottle (D-spraying). The maturation time and cycle of oyster mushrooms were compared between the two different spraying methods. The experimental environment was controlled at a temperature of 25 ± 1 °C and a relative humidity of 45 ± 2%. The results are as follows: Figure 2 As shown.

[0034] The results showed that SAP T-spraying treatment significantly promoted the growth of edible fungi P. ostreatus growth, Figure 2 (a) is P treated with D-spraying and SAP T-spraying on the eighth day (192h). ostreatus Phenotypic characteristics of the fruiting body. Top view: cap morphology; side view: stipe structure. Figure 2 Phenotypic analysis of a showed that P was sprayed with SAP T-spraying on the eighth day of cultivation. ostreatusThe specimens have reached maturity, with a stem length of 7.37 cm and a significantly increased cap area of ​​123.74 cm². In contrast, the specimens treated with traditional D-spraying are still in the formative stage, with a stem length of only 2.59 cm and a smaller cap area of ​​only 25.47 cm².

[0035] Figure 2 (b) shows the P process for D-spraying and SAP T-spraying. ostreatus The time difference in the four developmental stages (primordial stage, differentiation stage, formation stage, and maturity stage). Figure 2 b shows the P-processing of D-spraying and SAP T-spraying. ostreatus The time cycles for reaching different growth stages were as follows: Oyster mushrooms treated with SAP T-spraying reached the primordium stage in 72 hours, while those treated with D-spraying required 138 hours, making SAP T-spraying treatment 66 hours earlier than D-spraying. This accelerated growth continued in subsequent developmental stages: differentiation occurred at 108 hours, 48 ​​hours earlier than D-spraying; fruiting body formation (maturation stage) occurred at 168 hours, 21 hours earlier than D-spraying; and maturity occurred at 213 hours, 21 hours earlier than D-spraying. Notably, SAP T-spraying treatment continuously shortened the P (prototype) stage. ostreatus The growth time required to reach each key developmental milestone.

[0036] Figure 2 (cf) refers to P. ostreatus The cap area (c), stipe length (b), fresh weight (e), and moisture content (f) were compared, with the fresh weight and moisture content comparison time being 192 h. Phenotypic characterization was observed in five replicate experiments, with P receiving SAP T-spraying treatment. ostreatus The cap area was approximately 117.81 cm², which is 4.06 times that of the D-spraying treatment (29.01 cm²). Figure 2 c); the average stipe length was 7.09 cm, which was 2.01 times longer than that of the D-spraying treated stipe (3.52 cm). Figure 2 d); The average fresh weight at maturity was 60.14 g, significantly higher than the 36.19 g of the D-spraying group, representing a 66.18% increase in weight (see [reference needed]). Figure 2 e) The average moisture content was 83.24%, which was 3.16% higher than that of the D-spraying group (80.08%).

[0037] This demonstrates that SAP T-spraying has the ability to promote the growth of edible fungi.

[0038] Example 4 The deposition process was recorded on the underside of the leaves using a high-speed camera. The spray was emitted from a spray bottle or nozzle 30 cm away from the leaf. The high-speed camera captured the deposition process and results on the underside of the leaves at a frame rate of 2000 fps, with an image resolution of 1296×5800 pixels. Fresh leaves of *Tetracentron sinense* were collected and placed in water to simulate a real-world application scenario during the encirclement deposition. A 300 mL spray bottle was used as the spraying equipment. The nozzle pressure was controlled at 0 kV before spraying, and the experimental environment was controlled at a temperature of 25 ± 1 ℃ and a relative humidity of 45 ± 2%. The encirclement deposition density on the underside of the leaves was used to measure the encirclement deposition effect under different spraying conditions, i.e., the number of droplets deposited per unit area.

[0039] The relative standard deviation (RSD) of droplet deposition density is used to represent the uniformity of spray encirclement deposition. The back surface of the substrate is divided into six parts, and the deposition density of each part is measured and calculated according to the RSD formula.

[0040] Where S is the standard deviation and ¯x is the average value of the six sedimentary densities.

[0041] By using highly positively charged sprays generated by SAP T-spraying, this invention significantly improves the deposition efficiency of aqueous sprays containing insecticides, fungicides, plant growth regulators, and foliar fertilizers on superhydrophobic plant leaves.

[0042] In this embodiment, a 300 mL spray bottle was used to spray the solution onto the crop (forsythia leaves) through a superhydrophobic tube (SAP T-spraying). The spray solution included water-soluble 2,4-epibrassinolide, pyraclostrobin suspension, sodium nitrophenolate aqueous solution, and amino acid-containing water-soluble fertilizer. Control group 1 used a conventional electrostatic sprayer for solution spraying (D-spraying); Control group 2 used a superhydrophobic surface-enhanced spraying method, i.e., coating the inner wall of a PTFE or PMMA tube with hydrophobic nano-silica to create a superhydrophobic tube, and then spraying the solution onto the crop (forsythia leaves) through the superhydrophobic inner wall using a spray bottle (SHB T-spraying). The experimental results are as follows: Figure 3 As shown.

[0043] Figure 3 Image a shows an optical image of a Forsythia suspensa leaf and its contact angles on both sides, confirming the superhydrophobicity of the plant leaf.

[0044] Environmental scanning electron microscope (SEM) images of the blade surface ( Figure 3 b) The micro-nano structures on the leaf surface, which give the leaf superhydrophobicity and stomata located on the underside of the leaf, demonstrate the importance of deposition on the underside of the leaf, which is crucial for the utilization and absorption of nutrients.

[0045] Figure 3 c represents the specific ingredients of the four agricultural formulations used, including water-soluble 2,4-epibrassinolide (0.01%), pyraclostrobin suspension (30%), sodium nitrophenolate aqueous solution (1.8%), and amino acid-containing water-soluble fertilizer.

[0046] Figure 3 Figure d shows the surface tension test results of four pesticide formulation samples with water. It can be seen that the 2,4-epibrassinolide sample, diluted 1000 times, had the lowest surface tension, at only 32.8 mN·m. -1 All test samples, including those containing water, exhibited contact angles exceeding 150°, indicating that the tube surface possesses superhydrophobic and superoleophobic properties. However, the sliding angle of the diluent was in the range of 20-30°, suggesting that the formulated droplets exhibit significant adhesion characteristics on the superhydrophobic and superoleophobic surface. Improving the encapsulation deposition effect of low surface tension, high-adhesion droplets represents a breakthrough in this work.

[0047] like Figure 3 As shown in e, the CMR values ​​of D-spraying for H2O and the four pesticide formulations were -111.08, 2.31, -2.59, -2.44, and -1.24 nC g, respectively. -1 The CMR values ​​of SHB T-spraying were 224.43, 269.38, 146.15, 167.35, and 306.96 nC g, respectively. -1 The CMR values ​​of SAP T-spraying were 324.85, 336.29, 213.03, 316.08, and 459.37 nC g, respectively. -1 CMR comparison showed that SAP T-spraying consistently produced positively charged spray, and its CMR value was higher than that of D-spraying and SHBT-spraying.

[0048] SAP T-spraying exhibits superior deposition performance, significantly outperforming D-spraying and SHB T-spraying. Figure 3 gi).

[0049] On leaves of *Tetracentron sinense*, the dorsal deposition densities of the five D-spraying formulations were 0.39, 0.44, 0.28, 0.31, and 0.39 d·mm⁻¹, respectively.-2 SHB T-spraying improved these values ​​to 1.76, 0.86, 0.73, 1.23, and 1.93 d·mm. -2 SAP T-spraying further increased deposition rates, reaching 4.01, 2.69, 1.68, 1.85, and 4.11 d·mm. -2 ( Figure 3 j).

[0050] Notably, SAP T-spraying increased the deposition density on the underside of blades by 10.28, 6.11, 6.00, 5.97, and 10.54 times, respectively, far exceeding the threshold required for electrostatic spraying of deposition on the underside of blades. Furthermore, SAP T-spraying improved deposition uniformity and resulted in a lower relative standard deviation (RSD) value. Figure 3 k).

[0051] Therefore, SAP T-spraying has proven to be a versatile technique for stabilizing the positive charge properties of droplets and improving back deposition efficiency.

Claims

1. A super-dual-diameter pipe spraying method, comprising a spray bottle or a high-pressure spray gun, wherein droplets are sprayed out after passing through the super-dual-diameter inner wall of the super-dual-diameter pipe, i.e., super-dual-diameter pipe spraying, wherein, The superhydrophobic tube is a PMMA polymer tube with a superhydrophobic coating on its inner wall. The raw materials for preparing the superhydrophobic coating include TiO2 nanoparticles and hydrophobic epoxy resin.

2. The ultra-dual-channel spray method according to claim 1, wherein, The preparation method of the superhydrophobic tube includes: uniformly dispersing hydrophobic TiO2 nanoparticles in ethyl acetate, then adding hydrophobic epoxy resin at a mass ratio of 1:10 under magnetic stirring, and stirring continuously for 10 min to obtain a solution; The solution was then sprayed onto the inner wall of the PMMA polymer tube using a spray gun. After curing at room temperature for 24 hours, a robust superhydrophobic coating was formed, resulting in a superhydrophobic tube.

3. The ultra-dual-channel spray method according to claim 1, wherein, In the preparation method of the super dual-channel tube, the spray gun pressure is 0.1-0.2 MPa, the distance between the nozzle and the tube opening is 20-30 cm, the spray gun is sprayed for 5 seconds at each of the two tube openings before and after the tube, and the coating is sprayed evenly and has no cracks after drying.

4. The ultra-dual-channel spray method according to claim 1, wherein, The charge-to-mass ratio of the super dual-channel sprayer reaches 1845.11 nC·g. -1 .

5. The application of the super-dual-tube spray method according to any one of claims 1-4 in improving encirclement deposition efficiency.

6. The application according to claim 5, wherein, The application includes: using a spray bottle or high-pressure spray gun to spray a spray solution onto crops through an ultra-diffuse nozzle, wherein the spray solution is selected from at least one of water-soluble 2,4-epibrassinolide, pyraclostrobin suspension, sodium nitrophenolate aqueous solution, and amino acid-containing water-soluble fertilizer.

7. The application of the super dual-channel spray method according to any one of claims 1-4 in biomass degradation.

8. The application according to claim 7, wherein, The application includes collecting droplets sprayed by the super-dual-tube spray method and processing biomass feedstock to degrade the biomass therein.

9. The application according to claim 7, wherein, The biomass raw material includes at least one of cottonseed hulls, wheat bran, and corn cobs; and / or, the biomass includes at least one of lignin, cellulose, and hemicellulose.

10. The application of the super-dual-channel spray method according to any one of claims 1-4 in promoting fungal growth, comprising spraying water onto the surface of the substrate using the super-dual-channel spray method, followed by normal cultivation.

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