CN116462920B - Preparation method of nut shell/polyvinyl chloride composite material - Google Patents
Preparation method of nut shell/polyvinyl chloride composite material Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
The invention discloses a preparation method of a nut shell/polyvinyl chloride composite material, which comprises the following steps: the nut shell is used as a raw material, and the composite material is obtained by a hydrothermal treatment process, an enzyme treatment process, a stirring process after mixing and an ultrasonic process and then a vacuum hot press forming machine. The invention solves the defects of easy aggregation, poor interfacial compatibility and low mechanical property existing in the composite of the nut shells and the polyvinyl chloride by treating the nut shells, improves the compatibility of the nut shells and the polyvinyl chloride matrix, enhances the interfacial property of the nut shells and the polyvinyl chloride, ensures that the doping amount of the nut shells can reach 50 percent, greatly improves the recycling rate of the nut shells, and finds a new path for the application of the crop nut shells in the composite material.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a preparation method of a nut shell/polyvinyl chloride composite material.
Background
Composite materials are generally materials formed by combining thermoplastic polymers and renewable material fiber materials in a specific proportion, and sectional materials prepared by various processes including extrusion molding, compression molding, injection molding and the like have great significance in the fields of environmental protection and materials due to high strength, stability and low density.
In recent years, plant fibers have attracted researchers' interest due to their high availability, regenerability and biodegradability. Plant fibers have several advantages over conventional fibers, including lower cost, lower density, reusability, and good biocompatibility, plant fibers, agricultural materials, and biodegradable polymers, developing biodegradable wood-plastic composites. In addition, such green composites, consisting mainly of plant fibers and biopolymers, have good mechanical properties, remarkable manufacturing advantages, relatively low densities, making them suitable for industrial applications with the potential to replace synthetic polymeric materials. And is used to make various wood products such as street guards, floors, billboards, park tables, benches, walkways, etc.
Nut shells are a common biomass resource, are widely available and have high annual output, and are commonly regarded as agricultural waste. Meanwhile, in order to maximize development and reuse, nut shells are often incinerated directly or dumped into the field, causing serious environmental pollution and degradation of soil conditions. Therefore, it is important to develop techniques for efficiently utilizing and upgrading reconstituted nut shells.
Therefore, a method for efficiently and environmentally utilizing the plant fiber reinforced composite material is explored, so that not only can agricultural wastes be fully utilized, but also the production cost can be reduced. However, untreated nut shell fibers have hydrophilic properties and exhibit interfacial incompatibility with mechanical properties and microstructure during polymer synthesis. In order to solve the problem of interfacial bonding between the fibers and the matrix, the most common operation adopted is to treat the fibers, and alkali treatment can improve the adhesion between the fibers and the plasticized matrix, thereby enhancing the performance of the composite material. However, alkali treatment of plant fibers generates a large amount of waste products of chemical reagents, causing problems of environmental pollution and high recovery cost.
The hydrothermal treatment can effectively improve the performance of the plant fiber, including the dimensional stability, durability and corrosion resistance thereof, and form an environment-friendly treatment method. In the hydrothermal treatment, the closed type hydrothermal treatment not only increases the moisture content in the fiber and reduces cracking, but also enhances the fluidity of the polymer chains and reduces the activation energy of the polymer in the amorphous region, thereby improving the degradation rate and further reducing the energy consumption during the hydrothermal treatment.
Cellulases are a complex group of enzymes with synergistic properties, including endoglucanases, exoglucanases and beta-glucosidase. Endonucleases hydrolyze non-crystalline regions within cellulose molecules, cleaving long chain cellulose molecules, producing large numbers of small cellulose molecules with non-reducing ends. Xylanases can remove hemicellulose between fibrils and break bonds between hemicellulose and cellulose or lignin. It removes xylan from the fiber surface, thereby providing the plant fiber with a smoother surface and higher tensile strength. The combination of cellulases and xylanases has been shown to be effective for hydrolysis of cellulosic fibers due to their synergistic catalytic mechanism. In particular, xylanases hydrolyze hemicellulose on the surface of cellulose or in the amorphous areas of cellulose, clearing the barrier to cellulose from cellulase. By the synergistic action of the cellulase and xylanase, the cellulose fiber morphology can be adjusted, such as increasing fiber porosity and fiber swelling, thereby enhancing accessibility of cellulose.
Ultrasonic processing is increasingly used in the manufacture and processing of new materials due to its high efficiency, ease of operation, repeatability and controllability, including its correlation with naturally derived polymeric materials. Ultrasound involves a series of sparse, dense longitudinal waves that create a divergent, flat or focused sound field that produces vibrational energy through propagation of a medium that, when applied to a material, produces mechanical, acoustic, thermal effects.
Vacuum heating and pressurizing is a novel forming method, and combines the advantages of vacuum extrusion and hot extrusion processes. The material is heated to the required temperature in vacuum state, and then the upper and lower pressure heads move to compress and deform the workpiece, so that the material with certain plasticity is pressurized in a certain cavity, defects are reduced, grains are refined, the technological requirements of impurity removal, purification, high density and the like are met, and the product quality material is improved.
However, prolonged treatment can damage the nut shell structure itself, thereby reducing the mechanical properties of the composite. Therefore, it is of great significance in the art to develop a method of preparing a nut shell/polyvinyl chloride composite that both protects the nut shell strength and improves the compatibility with the substrate.
Disclosure of Invention
Aiming at the defects of the composite of the nut shells and the polymer matrix material, the invention provides a preparation method of the nut shells/polyvinyl chloride composite material, which is characterized in that the nut shells are treated and then are composited with the polyvinyl chloride, so that the aggregation of the nut shells is avoided, the interfacial compatibility between the nut shells and the polyvinyl chloride is improved, and the physical and mechanical properties of the obtained composite material are ensured.
The invention selects polyvinyl chloride as a polymer matrix, adopts low-cost nut shell fiber to replace wood fiber for reinforcing the polymer matrix, and prepares the nut shell/polyvinyl chloride composite material. In addition, the polyvinyl chloride has good processability, and provides a basis for preparing the green and environment-friendly nut shell/polyvinyl chloride composite material with high strength and excellent processability. Before compounding with polyvinyl chloride, the invention pre-treats the nut shells, and the material is obtained by a vacuum hot-press forming machine through a hydrothermal treatment process, an enzyme treatment process, a stirring process after mixing, an ultrasonic process and the like to solve the defects of easy aggregation, poor interface compatibility, low mechanical property and the like existing in the compounding of the nut shell plant fibers and the polyvinyl chloride.
The technical scheme of the invention is as follows:
a preparation method of a nut shell/polyvinyl chloride composite material is characterized by comprising the following steps:
step one, taking nut shells as raw materials, drying and crushing the nut shells, and sieving the dried nut shells with a 100-mesh sieve to obtain nut shell powder;
step two, a hydrothermal treatment process: placing nut shell powder in distilled water according to a certain proportion, and performing hydrothermal treatment in a closed heating container;
step three, enzyme treatment process: filtering, washing and drying the sediment treated in the second step after the combined reaction of cellulase and xylanase to obtain treated nut shell powder;
step four, stirring: adopting an electromagnetic stirring mode, and proportionally mixing the treated nut shell powder, polyvinyl chloride, attapulgite, a stabilizer and a coupling agent according to the proportion of 35-50 wt percent: 40-59 wt%: 5-15% wt%: 3-6 wt%: mixing 3-6 and wt percent, and adding deionized water with a certain proportion for stirring; firstly, manually stirring, then transferring the mixed solution into an electromagnetic stirring device, and uniformly mixing at the rotating speed of 450-550 rpm for 10-30 min;
step five, an ultrasonic process: the mixed solution obtained in the step four is further treated by an ultrasonic process;
step six, vacuum heating and pressurizing process: and (3) carrying out hot press molding on the precipitate obtained in the step (V) in a vacuum heating and pressurizing device.
In the first step, the nut shell is at least one of walnut shell, almond shell, hazelnut shell and pistachio shell.
Further, in the second step, the ratio of the nut shell powder to the distilled water is 100 g:1L-100 g:1.5L; the hydrothermal temperature is 100-120 ℃ and the time is 15-30 min.
Further, in step three, the enzymes are cellulase with an activity of 1.1X104U/g and xylanase with an enzyme activity of 2.8X105U/g, the ratio of cellulase to xylanase is 9:1, stirring 20-30 h under the optimal reaction condition of 60-75 ℃, stopping the reaction, and boiling the mixture for 8-12 min to inactivate the enzyme.
Further, in the fifth step, the ultrasonic wave adopts an intermittent mode with the frequency of 20kHz and the pause time of 5 seconds per ultrasonic wave, the amplitude is 45-75 percent, and the time is 10-30 minutes.
In the sixth step, the vacuum heating and pressurizing device is a vacuum hot-press forming machine, and mainly comprises a heating die and a hydraulic press device, wherein the heating temperature is 155-175 ℃. The material is characterized in that the processed nut shell mixture is placed between an upper die and a lower die, the dies are placed on a hot press forming table in a die closing mode, and after a certain time of high temperature and high pressure are used for solidification, the product is taken down. The forming technology has the advantages of high efficiency, good product quality, high dimensional accuracy, small influence by environment and the like, and is suitable for forming composite material products with large batch and high strength.
Furthermore, the preparation method of the obtained nut shell/polyvinyl chloride composite material can be made into different shapes, such as cuboid plates and the like, according to requirements.
The invention adopts the hydrothermal treatment process, the enzyme treatment process, the stirring process after mixing, the ultrasonic process and the like to treat the nut shell plant fiber, the hydroxyl content and the surface polarity of the fiber are reduced by the hydrothermal treatment, and the compatibility between the natural fiber and the matrix is enhanced, so that the high-quality and thermally stable composite material is produced. By the synergistic action of the cellulases and xylanases, the cellulose fiber morphology can be tuned, such as to increase fiber porosity and fiber swelling, thereby enhancing accessibility of cellulose, and mechanical and cavitation effects in the agitation and sonication process (ultrasound increases the porous structure of the nut shell fibers from hydrophilic to superhydrophobic) can sustain impact and effectively remove amorphous deposits in the nut shell fiber pores. The hydrophobic polymer can be uniformly connected to the surface of the nut shell fibers to prevent the nut shell fibers from gathering, and promote the mutual winding between the nut shell fibers and the polyvinyl chloride matrix, so that the compatibility of the nut shell and the polyvinyl chloride of the polymer matrix is improved, the interfacial bonding capability of the nut shell and the polyvinyl chloride is improved, and the mechanical property of the composite material are greatly improved.
The method disclosed by the invention has the advantages that the adding amount of the nut shells in the composite material can be improved to 50% at the highest through the treatment and the vacuum heating and pressurizing processes, the recycling rate of the nut shells is improved, and a new path is found for the application of agricultural waste nut shells in the field of composite materials. The obtained nut shell can completely meet the mechanical property requirement of the composite material, can be used in the fields of home, outdoor construction and the like, and the polyvinyl chloride can be recycled and reused, so that the environment friendliness is good.
The beneficial effects of the invention are as follows:
1. the invention overcomes the defects of easy self aggregation and poor compatibility with the polyvinyl chloride of the polymer matrix by processing the nut shells, improves the compatibility of the nut shells and the polyvinyl chloride matrix, improves the interface performance of the nut shells and the polyvinyl chloride, ensures that the doping amount of the nut shells can reach 50 percent, greatly improves the recycling rate of the nut shells, and provides a new path for the application of the agricultural waste nut shells in the field of composite materials.
2. The raw materials used in the invention are wide in sources and low in price, the preparation process is simple, economic and green, the obtained composite material is excellent in mechanical property and mechanical property, has good application prospect in the fields of building decoration, landscape, automobiles and the like, and finds a new utilization value for agricultural wastes.
Drawings
FIG. 1 is the results of mechanical and abrasion resistance tests for examples one to four and comparative examples one to four;
FIG. 2 is an impact profile micro-morphology of a composite of comparative example;
FIG. 3 is an impact profile micro-morphology of a comparative example four composite;
FIG. 4 is a microscopic morphology of a wear section of a composite of comparative example;
FIG. 5 is a microstructure of a wear section of a comparative example four composite.
Description of the embodiments
The invention will now be further illustrated by the following specific examples, it being understood that the following description is illustrative only and is not limiting in any way.
In the examples described below, each of the raw materials is commercially available.
Examples
The nut shell/polyvinyl chloride composite material is prepared according to the following method, and the steps are as follows:
a. drying walnut shells in a blast drying oven at 60 ℃ for 24h, crushing by an ultrafine crusher, and sieving by a 100-target standard sieve to obtain walnut shell powder;
b. the hydrothermal treatment process comprises the following steps: dissolving walnut shell powder in 100 g/1L distilled water, and treating at 110deg.C for 25min in a closed heating container;
c. enzyme treatment process: cellulase and xylanase in combination activity 9: under the condition of 68 ℃ with the walnut shell powder, carrying out reaction 24h, filtering, washing and drying to obtain the treated walnut shell powder;
d. stirring: adopts an electromagnetic stirring mode, and the proportion of the walnut shell powder, the polyvinyl chloride, the stabilizer, the coupling agent and the attapulgite after treatment is 40:49:8:3:3, after mixing, 1g of: stirring 20ml of deionized water; firstly, manually stirring, then transferring the mixed solution into an electromagnetic stirring device, and uniformly mixing at the rotating speed of 500 rpm for 20 min;
e. ultrasonic process: the mixed solution obtained by uniformly stirring is further subjected to an intermittent mode with the frequency of 20kHz and the pause time of 1s every 5s of ultrasonic waves, and the amplitude is 60 percent and the time is 25 minutes; filtering the supernatant liquid of the mixed solution by a suction filtration mode after ultrasonic treatment, drying in a blast drying oven at 60 ℃, and grinding the particle size to 100 meshes;
d. and (3) placing the treated mixed material between an upper die and a lower die, closing the dies, placing the dies in a hot press forming machine, heating to 170 ℃, and taking down the product to be a cuboid plate after vacuum high-temperature curing for 15 min.
Examples
The nut shell/polyvinyl chloride composite material is prepared according to the following method, and the steps are as follows:
a. drying the almond hull in a blast drying oven at 60 ℃ for 24h, crushing by an ultrafine crusher, and sieving by a 100-target standard sieve to obtain almond hull powder;
b. the hydrothermal treatment process comprises the following steps: dissolving almond hull powder in 100 g/1L distilled water, and treating at 110deg.C for 25min in a closed heating container;
c. enzyme treatment process: cellulase and xylanase in ratio 9:1, reacting the almond hull powder with the almond hull powder at 68 ℃ under the optimal reaction condition of 24-h, filtering, washing and drying to obtain the treated almond hull powder;
d. stirring: adopts an electromagnetic stirring mode, and the proportion of the almond shell powder, the polyvinyl chloride, the stabilizer, the coupling agent and the attapulgite after treatment is 40:49:8:3:3, after mixing, 1g of: stirring 20ml of deionized water; firstly, manually stirring, then transferring the mixed solution into an electromagnetic stirring device, and uniformly mixing at the rotating speed of 500 rpm for 20 min;
e. ultrasonic process: the mixed solution obtained by uniformly stirring is further subjected to an intermittent mode with the frequency of 20kHz and the pause time of 1s every 5s of ultrasonic waves, and the amplitude is 60 percent and the time is 25 minutes; filtering the supernatant liquid of the mixed solution by a suction filtration mode after ultrasonic treatment, drying in a blast drying oven at 60 ℃, and grinding the particle size to 100 meshes;
d. and (3) placing the treated mixed material between an upper die and a lower die, closing the dies, placing the dies in a hot press forming machine, heating to 170 ℃, and taking down the product to be a cuboid plate after vacuum high-temperature curing for 15 min.
Examples
The nut shell/polyvinyl chloride composite material is prepared according to the following method, and the steps are as follows:
a. drying the hazelnut shell in a blast drying oven at 60 ℃ for 24h, crushing by an ultrafine crusher, and sieving by a 100-target standard sieve to obtain hazelnut shell powder;
b. the hydrothermal treatment process comprises the following steps: dissolving hazelnut shell powder in 100 g/1L distilled water, and treating at 110deg.C for 25min in a closed heating container;
c. enzyme treatment process: cellulase and xylanase in ratio 9:1, reacting with hazelnut shells for 24 hours at 68 ℃ under the optimal reaction condition, filtering, washing and drying to obtain the processed hazelnut shell powder;
d. stirring: the method adopts an electromagnetic stirring mode, and the proportion of the hazelnut shell powder, polyvinyl chloride, the stabilizer, the coupling agent and the attapulgite after treatment is 40:49:8:3:3, after mixing, 1g of: stirring 20ml of deionized water; firstly, manually stirring, then transferring the mixed solution into an electromagnetic stirring device, and uniformly mixing at the rotating speed of 500 rpm for 20 min;
e. ultrasonic process: the mixed solution obtained by uniformly stirring is further subjected to an intermittent mode with the frequency of 20kHz and the pause time of 1s every 5s of ultrasonic waves, and the amplitude is 60 percent and the time is 25 minutes; filtering the supernatant liquid of the mixed solution by a suction filtration mode after ultrasonic treatment, drying in a blast drying oven at 60 ℃, and grinding the particle size to 100 meshes;
d. and (3) placing the treated mixed material between an upper die and a lower die, closing the dies, placing the dies in a hot press forming machine, heating to 170 ℃, and taking down the product to be a cuboid plate after vacuum high-temperature curing for 15 min.
Examples
The nut shell/polyvinyl chloride composite material is prepared according to the following method, and the steps are as follows:
a. drying the pistachio nuts in a 60 ℃ blast drying oven for 24h, crushing by an ultrafine crusher, and sieving by a 100-target standard sieve to obtain pistachio nut shell powder;
b. the hydrothermal treatment process comprises the following steps: dissolving the pistachio nut shell powder in distilled water according to the ratio of 100g to 1L, and treating for 25min at the hydrothermal temperature of 110 ℃ in a closed heating container;
c. enzyme treatment process: cellulase and xylanase in ratio 9:1, reacting the dried pistachio nut shell powder with the pistachio nut shell powder at 68 ℃ under the optimal reaction condition of 24-h, filtering, washing and drying to obtain the processed pistachio nut shell powder;
d. stirring: adopting an electromagnetic stirring mode, and according to the proportion of the processed pistachio nut shell powder, polyvinyl chloride, a stabilizer, a coupling agent and attapulgite being 40:49:8:3:3, after mixing, 1g of: stirring 20ml of deionized water; firstly, manually stirring, then transferring the mixed solution into an electromagnetic stirring device, and uniformly mixing at the rotating speed of 500 rpm for 20 min;
e. ultrasonic process: the mixed solution obtained by uniformly stirring is further subjected to an intermittent mode with the frequency of 20kHz and the pause time of 1s every 5s of ultrasonic waves, and the amplitude is 60 percent and the time is 25 minutes; filtering the supernatant liquid of the mixed solution by a suction filtration mode after ultrasonic treatment, drying in a blast drying oven at 60 ℃, and grinding the particle size to 100 meshes;
d. and (3) placing the treated mixed material between an upper die and a lower die, closing the dies, placing the dies in a hot press forming machine, heating to 170 ℃, and taking down the product to be a cuboid plate after vacuum high-temperature curing for 15 min.
Comparative example one
a. Drying walnut shells in a blast drying oven at 60 ℃ for 24h, crushing by an ultrafine crusher, and sieving by a 100-target standard sieve to obtain walnut shell powder;
b. stirring: adopts an electromagnetic stirring mode, and the proportion of the walnut shell powder, the polyvinyl chloride, the stabilizer, the coupling agent and the attapulgite after treatment is 40:49:8:3:3, after mixing, 1g of: stirring 20ml of deionized water; firstly, manually stirring, then transferring the mixed solution into an electromagnetic stirring device, and uniformly mixing at the rotating speed of 500 rpm for 20 min;
c. ultrasonic process: the mixed solution obtained by uniformly stirring is further subjected to an intermittent mode with the frequency of 20kHz and the pause time of 1s every 5s of ultrasonic waves, and the amplitude is 60 percent and the time is 25 minutes; filtering the supernatant liquid of the mixed solution by a suction filtration mode after ultrasonic treatment, drying in a blast drying oven at 60 ℃, and grinding the particle size to 100 meshes;
d. and (3) placing the treated mixed material between an upper die and a lower die, closing the dies, placing the dies in a hot press forming machine, heating to 170 ℃, and taking down the product to be a cuboid plate after vacuum high-temperature curing for 15 min.
Comparative example two
a. Drying walnut shells in a blast drying oven at 60 ℃ for 24 hours, crushing by an ultrafine crusher, and sieving by a 100-target standard sieve to obtain walnut shell powder;
b. the hydrothermal treatment process comprises the following steps: dissolving the pistachio nut shell powder in distilled water according to the ratio of 100g to 1L, and treating for 25min at the hydrothermal temperature of 110 ℃ in a closed heating container;
c. stirring: adopts an electromagnetic stirring mode, and the proportion of the walnut shell powder, the polyvinyl chloride, the stabilizer, the coupling agent and the attapulgite after treatment is 40:49:8:3:3, after mixing, 1g of: stirring 20ml of deionized water; firstly, manually stirring, then transferring the mixed solution into an electromagnetic stirring device, and uniformly mixing at the rotating speed of 500 rpm for 20 min;
d. ultrasonic process: the mixed solution obtained by uniformly stirring is further subjected to an intermittent mode with the frequency of 20kHz and the pause time of 1s every 5s of ultrasonic waves, and the amplitude is 60 percent and the time is 25 minutes; filtering the supernatant liquid of the mixed solution by a suction filtration mode after ultrasonic treatment, drying in a blast drying oven at 60 ℃, and grinding the particle size to 100 meshes;
e. and (3) placing the treated mixed material between an upper die and a lower die, closing the dies, placing the dies in a hot press forming machine, heating to 170 ℃, and taking down the product to be a cuboid plate after vacuum high-temperature curing for 15 min.
Comparative example three
a. Drying walnut shells in a blast drying oven at 60 ℃ for 24h, crushing by an ultrafine crusher, and sieving by a 100-target standard sieve to obtain walnut shell powder;
b. enzyme treatment process: cellulase and xylanase in ratio 9:1, reacting with walnut shell powder for 24 hours at 68 ℃ under the optimal reaction condition, filtering, washing and drying to obtain the treated walnut shell powder;
c. stirring: adopts an electromagnetic stirring mode, and the proportion of the walnut shell powder, the polyvinyl chloride, the stabilizer, the coupling agent and the attapulgite after treatment is 40:49:8:3:3, after mixing, 1g of: stirring 20ml of deionized water; firstly, manually stirring, then transferring the mixed solution into an electromagnetic stirring device, and uniformly mixing at the rotating speed of 500 rpm for 20 min;
d. ultrasonic process: the mixed solution obtained by uniformly stirring is further subjected to an intermittent mode with the frequency of 20kHz and the pause time of 1s every 5s of ultrasonic waves, and the amplitude is 60 percent and the time is 25 minutes; filtering the supernatant liquid of the mixed solution by a suction filtration mode after ultrasonic treatment, drying in a blast drying oven at 60 ℃, and grinding the particle size to 100 meshes;
e. and (3) placing the treated mixed material between an upper die and a lower die, closing the dies, placing the dies in a hot press forming machine, heating to 170 ℃, and taking down the product to be a cuboid plate after vacuum high-temperature curing for 15 min.
Comparative example four
a. Drying walnut shells in a blast drying oven at 60 ℃ for 24h, crushing by an ultrafine crusher, and sieving by a 100-target standard sieve to obtain walnut shell powder;
b. stirring: adopts an electromagnetic stirring mode, and the proportion of walnut shell powder, polyvinyl chloride, a stabilizer, a coupling agent and attapulgite is 40:49:8:3:3, after mixing, 1g of: stirring 20ml of deionized water; the method comprises the steps of (1) firstly, manually stirring, transferring the mixed solution into an electromagnetic stirring device, uniformly mixing at 500 rpm for 20 min, filtering the supernatant of the mixed solution in a suction filtration mode, drying in a blast drying oven at 60 ℃, and grinding the supernatant to 100 meshes;
c. and (3) placing the treated mixed material between an upper die and a lower die, closing the dies, placing the dies in a hot press forming machine, heating to 170 ℃, and taking down the product to be a cuboid plate after vacuum high-temperature curing for 15 min.
The composites of the above examples and comparative examples were subjected to performance verification as follows:
bending performance test
Test sample test is carried out by referring to GB/T9341-2008 test, the test sample size is 80 mm multiplied by 10 multiplied by mm multiplied by 4 mm, the span is 64 mm, the loading speed is 2 mm/min, an E43.104 microcomputer control electronic universal testing machine (Meite industrial system (China) Co., ltd.) is adopted for testing, and the test result under 5 times of test is recorded to obtain the average value.
Tensile Property test
Test sample test is carried out by referring to GB/T1040.1-2006 test, the test sample size is 160 mm multiplied by 10 multiplied by mm multiplied by 4 mm, the loading speed is 2 mm/min, an E43.104 microcomputer control electronic universal testing machine (Meite industrial system (China) Co., ltd.) is adopted for testing, and the test result under 5 times of tests is recorded to obtain an average value.
Impact strength test
Test sample test is carried out by referring to GB/T1043.1-2008 test, the test sample size is 80 mm multiplied by 10 multiplied by mm multiplied by 4 mm, pendulum energy is 1J, a G-P01 type simple beam impact tester (Kroney (Beijing) instruments and meters Co., ltd.) is adopted for test, and the test result under 5 times of test is recorded to obtain an average value.
Microscopic topography analysis
The impact section and the microscopic morphology of the worn surface of the composite material were observed by using a Japanese Hitachi S-3400N scanning electron microscope, and all samples were subjected to a metal spraying treatment for 60 seconds.
Wear Performance test
Test sample abrasive wear properties of the composite materials were tested with reference to ASTM-G65-16 (2021) using an MLG-130 dry abrasive rubber wheel abrasive wear tester. The test abrasive is dry sand, collected in the Lanzhou section of yellow river, washed and air-dried, and filtered by a 36-mesh screen (0.5 mm aperture). The hardness of the rubber wheel of the testing machine is 60 (Shore hardness), the diameter is 228.6 and mm, and the rotating speed of the rubber wheel is 200 and r/min. The abrasion time of each sample is 3 min, the mass of each sample before and after abrasion is measured by an analytical balance, the surface of each sample is cleaned by absolute ethyl alcohol before and after the test and is naturally air-dried, the average value is obtained after each group of test is repeated for 3 times, the specific abrasion rate is calculated according to the formula (1),
(1)
wherein: m is m 1 Mg is the mass before abrasion
m 2 For the quality after abrasion, mg
L is the sliding distance, m
F is the applied load, N
ρ is the sample density, g.cm -3
Conclusion:
conclusion 1: the results of the flexural property, tensile property, impact property and abrasion resistance of the products obtained in the first, comparative examples and fourth examples by using the standard methods in the industry are shown in fig. 1, and the mechanical properties of the composite material prepared from the nut shell reinforced polyvinyl chloride are better than those of the composite material prepared from the nut shell reinforced polyvinyl chloride without treatment, which indicates that the nut shell powder can replace the single treatment method after treatment.
Conclusion II: the results of testing the bending property, the tensile property, the impact property and the abrasion resistance of the products by adopting standard testing methods in the industry from the first example to the fourth example are shown in the figure 1, and the embodiment of the invention can improve the interfacial compatibility of the nut shell and the polyvinyl chloride of the polymer matrix, so that the interfacial bonding capability of the nut shell and the polyvinyl chloride is improved, and the mechanical property of the composite material is effectively improved. The bending strength of the wood-plastic composite material can be improved by 20%, the tensile strength can be improved by 27% and the impact strength can be improved by 57% by adopting the test results of bending property, tensile property, impact property and abrasion resistance of the products by adopting the standard test methods in the industry from the first example and the third example as shown in figure 1.
Conclusion III: the results of impact section test on the materials by adopting a scanning electron microscope in the first and fourth comparative examples are shown in fig. 2 and 3, when the nut shell powder is subjected to the stirring process and the ultrasonic process, the prepared composite material has more broken walnut shell powder particles and no filler pull-out or drop, which indicates that the walnut shell powder has high bonding strength with the polyvinyl chloride matrix, the filler drop occurs less on the bonding surface under the impact load, and the damage form is mainly the integral breaking of the composite material. Analysis shows that the fiber-closed void structure can be opened by ultrasonic pretreatment, so that the microfibers can be rapidly expanded, suddenly closed and oscillated under the action of the ultrasonic, the accessibility of the fibers to participate in the reaction is improved, the condition is provided for the sufficient combination of the polyvinyl chloride and the walnut shell powder particles, the interaction between the walnut shell powder and the matrix is further enhanced, and a tighter combination interface is formed. Secondly, research proves that ultrasonic waves are an effective method for destroying agglomeration and stress concentration, and the porosity in the composite material is reduced due to a tight joint surface, so that the material is more uniform, the stress concentration point in the material is further reduced, and finally the impact strength of the composite material is enhanced.
Conclusion IV: from the results of wear surface testing of the materials in comparative examples one and four using a scanning electron microscope as shown in fig. 3 and 4, the wear surface microscopic morphology of the walnut shell/polyvinyl chloride composite material in comparative example four was observed to be mainly lamellar cutting and filler flaking in the form of wear, while fewer micropores and pits were visible in the wear surface. The appearance of the wearing surface of the first comparative example is smoother, and the surface has more furrows and furrows, which indicates that the wearing form of the walnut shell/polyvinyl chloride composite material is mainly micro-ploughing and adhesive wearing, and has better wear resistance. Analysis shows that after ultrasonic pretreatment, walnut shell powder particles are thinned and the surface is coarser after etching, so that more effective acting areas are formed between the walnut shell powder particles and a polyvinyl chloride matrix easily, the effective adhesion of the polyvinyl chloride on the surface of the walnut shell powder is promoted, the interaction between a matrix phase and an enhanced phase interface is enhanced, the interfacial compatibility of the walnut shell powder and the polyvinyl chloride is enhanced, and when the walnut shell powder is acted by external force, load can be effectively transferred between the matrix and the walnut shell powder, so that the wear resistance of the walnut shell/polyvinyl chloride composite material is enhanced.
Conclusion five: as can be seen from the data of fig. 1, the flexural strength, tensile strength, impact resistance, and abrasion resistance of the composite material are enhanced with processing.
The invention is not a matter of the known technology.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (6)
1. A preparation method of a nut shell/polyvinyl chloride composite material is characterized by comprising the following steps:
step one, taking nut shells as raw materials, drying and crushing the nut shells, and sieving the dried nut shells with a 100-mesh sieve to obtain nut shell powder;
step two, a hydrothermal treatment process: placing nut shell powder in distilled water according to a certain proportion, and performing hydrothermal treatment in a closed heating container;
step three, enzyme treatment process: filtering, washing and drying the sediment treated in the second step after the combined reaction of cellulase and xylanase to obtain treated nut shell powder;
step four, stirring: adopting an electromagnetic stirring mode, and proportionally mixing the treated nut shell powder, polyvinyl chloride, attapulgite, a stabilizer and a coupling agent according to the proportion of 35-50 wt percent: 40-59 wt%: 5-15% wt%: 3-6 wt%: mixing 3-6 and wt percent, and adding deionized water with a certain proportion for stirring; firstly, manually stirring, then transferring the mixed solution into an electromagnetic stirring device, and uniformly mixing at the rotating speed of 450-550 rpm for 10-30 min;
step five, an ultrasonic process: the mixed solution obtained in the step four is further treated by an ultrasonic process;
step six, vacuum heating and pressurizing process: and (3) carrying out hot press molding on the precipitate obtained in the step (V) in a vacuum heating and pressurizing device.
2. The method of preparing a nut shell/polyvinyl chloride composite material as claimed in claim 1, wherein: the nut shell is at least one of walnut shell, almond shell, hazelnut shell and pistachio shell.
3. The method for preparing the nut shell/polyvinyl chloride composite material according to claim 1, wherein the method comprises the following steps: in the second step, the ratio of the nut shell powder to the distilled water is 100 g:1L-100 g:1.5L; the hydrothermal temperature is 100-120 ℃ and the time is 15-30 min.
4. The method for preparing the nut shell/polyvinyl chloride composite material according to claim 1, wherein the method comprises the following steps: in the third step, the enzyme activity is 1.1X104U/g of cellulase and the enzyme activity is 2.8X105U/g of xylanase, and the ratio of the cellulase to the xylanase is 9:1, stirring 20-30 h under the optimal reaction condition of 60-75 ℃, stopping the reaction, and boiling the mixture for 8-12 min to inactivate the enzyme.
5. The method for preparing the nut shell/polyvinyl chloride composite material according to claim 1, wherein the method comprises the following steps: in the fifth step, the ultrasonic wave adopts an intermittent mode with the frequency of 20kHz, the pause of 1s for 5 seconds per ultrasonic wave, the amplitude of 45-75 percent and the time of 10-30 minutes.
6. The method for preparing the nut shell/polyvinyl chloride composite material according to claim 1, wherein the method comprises the following steps: in the sixth step, the vacuum heating and pressurizing device is a vacuum hot-press forming machine and mainly comprises a heating die and a hydraulic press device, wherein the heating temperature is 155-175 ℃.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005199133A (en) * | 2004-01-13 | 2005-07-28 | Shiga Pref Gov | Rice hull treating method |
| CN102796332A (en) * | 2012-08-28 | 2012-11-28 | 云南鑫乾矿业有限公司 | Polyvinyl chloride/modified nut shell powder composite material and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005199133A (en) * | 2004-01-13 | 2005-07-28 | Shiga Pref Gov | Rice hull treating method |
| CN102796332A (en) * | 2012-08-28 | 2012-11-28 | 云南鑫乾矿业有限公司 | Polyvinyl chloride/modified nut shell powder composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Physical, mechanical and abrasive wear behavior of attapulgite reinforced walnut shell/PVC composites;Yang, JQ et al.;《Journal of Polymer Research》;第29卷(第12期);第522页 * |
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