CN111171450A - High-impact-resistance and high-load-bearing polypropylene composite material, and preparation method and application thereof - Google Patents
High-impact-resistance and high-load-bearing polypropylene composite material, and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 73
- -1 polypropylene Polymers 0.000 title claims abstract description 41
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 38
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 28
- 239000000945 filler Substances 0.000 claims abstract description 24
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- 238000012986 modification Methods 0.000 claims abstract description 7
- 230000004048 modification Effects 0.000 claims abstract description 7
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- 239000004033 plastic Substances 0.000 claims description 17
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 16
- 238000001746 injection moulding Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
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- 238000001035 drying Methods 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C08K7/00—Use of ingredients characterised by shape
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- C08K7/10—Silicon-containing compounds
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- C08K9/00—Use of pretreated ingredients
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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Abstract
The invention discloses a high-impact-resistance and high-bearing polypropylene composite material which is prepared from a raw material composition, wherein the raw material composition comprises the following components in parts by weight: 100 parts by weight of polypropylene, 5-20 parts by weight of modified filler and 5-45 parts by weight of modified reinforcing fiber; the modified filler and the modified reinforcing fiber are both subjected to surface modification treatment by adopting a silane coupling agent. The method can reduce the use of matrix resin, achieve higher performance index, realize high bearing capacity and high toughness, and ensure bright color and low cost of products. The invention also discloses a preparation method and application of the high-impact-resistance and high-bearing polypropylene composite material.
Description
Technical Field
The invention relates to a high-molecular composite material, in particular to a high-impact-resistance and high-bearing polypropylene composite material, and a preparation method and application thereof.
Background
The plastic tray is a logistics unit matched with logistics equipment such as a forklift, a goods shelf and the like. The tray is widely applied to the fields of production, transportation, storage, circulation and the like, and is one of necessary logistics devices in modern logistics storage. Preliminary investigation of the China Committee for Pallet Special Committee of Committee for Logistics and procurement: china now has about 5000-7000 million trays of various kinds, and the annual output increases by about 2000 million. Wherein the wooden flat pallet accounts for about 90 percent, the plastic flat pallet accounts for 8 percent, and the steel pallet, the composite material pallet and the paper pallet account for 2 percent in total. The composite material flat tray and the plastic tray have a large rising ratio. The development of the formula technology of the hybrid composite reinforced polypropylene plastic tray not only improves the performance of the plastic tray and reduces the manufacturing cost of a company, but also has superiority in many aspects compared with the traditional wood tray, such as light weight, moisture resistance, corrosion resistance, worm damage resistance and the like, but the plastic tray also has the defects of weak bearing capacity, poor impact toughness and the like. Therefore, the development of the formulation technology of the high-bearing and high-impact plastic pallet has important significance for the development of the modern logistics industry.
CN104045900B discloses a plastic composite material for a pallet, which mainly comprises the following components in parts by weight: high density polyethylene or polypropylene: 70-85; sorbitan monostearate: 2.0 to 3.0; polytetrafluoroethylene: 0.5 to 1.0; ethylene-methacrylic acid copolymer: 2.0 to 5.0; silane coupling agent: 0.5 to 0.8; nano inorganic filler: 5.0 to 10; synthesizing rubber: 10-13; fiber: 8.0 to 12; flame retardant: 2.0 to 5.0; antioxidant: 1.0 to 2.0. The anti-cracking and anti-impact performance of the material is improved by adding the sorbitan monostearate and the polytetrafluoroethylene to perform combined action, so that a product prepared from the composite material has higher anti-cracking and anti-impact performance after falling; the ethylene-methacrylic acid copolymer, the sorbitan monostearate and the polytetrafluoroethylene are added for composite use, so that the Shore hardness of the material can reach over 90, and the method is a beneficial attempt in the field. However, the matrix resin in the material is used in a high amount, and the bearing capacity and the toughness are still required to be improved.
Disclosure of Invention
The invention aims to provide a high-impact-resistance and high-bearing polypropylene composite material, a preparation method and application thereof, which can reduce the use of matrix resin, achieve higher performance index, realize high bearing, high toughness and low cost.
The high impact resistance and high load bearing polypropylene composite material is prepared from a raw material composition, wherein the raw material composition comprises the following components in parts by weight: 100 parts by weight of polypropylene, 5-20 parts by weight of modified filler and 5-45 parts by weight of modified reinforcing fiber; the modified filler and the modified reinforcing fiber are both subjected to surface modification treatment by adopting a silane coupling agent.
Further, the raw material composition comprises: 100 parts by weight of polypropylene, 5 parts by weight of modified filler and 5 parts by weight of modified reinforcing fiber.
Further, the surface modification method of the modified filler comprises the following steps: adding a silane coupling agent diluted by absolute ethyl alcohol into a filling agent, wherein the adding amount of the silane coupling agent is 0.8-1% of the mass of the filling agent, and the mass ratio of the absolute ethyl alcohol to the silane coupling agent is (9): 1, stirring and mixing uniformly in a high-speed mixer for 5-30 min; the filler is superfine talcum powder, nano calcium carbonate, mica powder or nano clay.
Further, the surface modification method of the modified reinforced fiber comprises the following steps: adding a silane coupling agent diluted by absolute ethyl alcohol into the reinforced fiber, wherein the adding amount of the silane coupling agent is 0.8-1% of the mass of the reinforced fiber, and the mass ratio of the absolute ethyl alcohol to the silane coupling agent is 9: 1, stirring and mixing uniformly in a high-speed mixer for 5-30 min, wherein the reinforcing fiber is wollastonite fiber, basalt short fiber or chopped carbon fiber.
A preparation method of a high impact resistance and high load bearing polypropylene composite material comprises the following steps:
firstly, carrying out surface modification treatment on a filler and a reinforcing fiber by using a silane coupling agent, and then weighing raw materials according to the raw material composition of any one of claims 1-5;
blending the raw materials in a high-speed mixer for 1-5 min, and drying to obtain a mixed material;
and step three, extruding and granulating by using a double-screw extruder to obtain granules, wherein the temperature of each area of the double-screw extruder is set as follows: the temperature of the first area is 70-90 ℃, the temperature of the second area is 110-130 ℃, the temperature of the third area is 150-170 ℃, the temperature of the fourth area is 170-190 ℃, and the temperature of the fifth-IX area is 190-210 ℃;
step four, injection molding, namely performing injection molding on the granules by using an injection molding machine to obtain the high-impact-resistance and high-bearing polypropylene composite material, wherein the temperature of each zone of the injection molding machine is set as follows: 200 to 220 ℃, 210 to 230 ℃ and 190 to 210 ℃.
The high impact resistance and high bearing capacity polypropylene composite material is applied to plastic trays.
The wollastonite fiber is selected from a plurality of fiber raw materials as a reinforcing fiber raw material, is a natural needle-shaped white crystal, has higher whiteness and good surface property, and has a special needle-shaped wollastonite fiber structure, so that the wollastonite fiber has superior performance in the aspect of rigidity of a composite material. The surface of the wollastonite fiber is treated by the silane coupling agent, so that the hydrophobicity and the organophilic property of the wollastonite fiber can be improved, and the dispersibility of the wollastonite fiber in polypropylene is improved.
According to the invention, the modified filler and the modified reinforcing fiber are added into the polypropylene, so that the tensile strength and the impact strength of the composite material are not greatly influenced, but under the condition of a certain addition amount of the modified filler, the bending strength of the composite material is increased along with the increase of the content of the modified reinforcing fiber. Therefore, the obtained composite material is used as a plastic tray, the bending strength of the composite material is improved on the premise of ensuring the original tensile strength and impact strength of the polypropylene material, and the plastic tray has the advantages of high bearing capacity, high toughness and low cost.
According to the invention, the cheap modified filler and modified reinforcing fiber are added, so that the use amount of matrix resin is reduced, higher performance indexes are achieved, and the aims of high bearing capacity, high toughness, low cost and the like are fulfilled.
The preparation method provided by the invention is simple in process flow and suitable for large-scale industrial production.
Drawings
FIG. 1 is an SEM image of a composite material of example two;
FIG. 2 is a second SEM image of the composite material of the second embodiment;
FIG. 3 is an SEM image of a composite material of example III;
fig. 4 is an SEM image of the composite material of example four.
Detailed Description
The invention is described in detail below with reference to the accompanying drawings.
The sources of the raw materials used in the present invention are shown in table 1.
TABLE 1 sources of raw materials
| Raw materials | Model number | Producing area |
| Polypropylene | K8303 | Duyazi petrochemical Co Ltd |
| Talcum powder | SK-6500P | Liaoning essence New Material Co Ltd |
| Wollastonite fiber | AT-0025 | Jiangxi Keyuan powder Co Ltd |
| Coupling agent | Silane coupling agent KH-171 | Huai' an and Yuan chemical Co Ltd |
| Anhydrous ethanol | Analytical purity | Chengdu Kelong chemical reagent plant |
The main equipment and instruments involved in processing and testing the material properties of the present invention are shown in Table 2.
TABLE 2 apparatus and instruments
| Device name | Model number | Producing area |
| High-speed mixer | SHR-1.0 | Jiangsu white bear machinery Co Ltd |
| Double-screw extruder | TSE-30A | Fuster Polymer Equipment Ltd, Nanjing Ruiya |
| Plastic injection molding machine | TTI-956 | Towa machinery Co., Ltd |
| Notch sampling machine | XQZ-J | Chengdi-Ci-a detection Instrument Co Ltd |
| Microcomputer controlled universal tension tester | CMT6104 | Meits Industrial System (China) Co., Ltd |
| Pendulum impact testing machine | ZBC1400-B | Meits Industrial System (China) Co., Ltd |
| Scanning electron microscope and energy spectrometer | JSM-6460LV | Japan electronic Co., Ltd |
| Electric heating vacuum drying oven | DZF-6050AB | Tianjin City of Industrial and electrical works |
The proportions of the raw material compositions of the first, second, third, fourth and fifth examples are shown in Table 3.
TABLE 3 example composition ratios of first, second, third, fourth and fifth raw materials
| Polypropylene/g | Talcum powder/g | Wollastonite fiber/g | Silane coupling agent KH-171/ml | |
| Comparative example | 1000 | 0 | 0 | 0 |
| Example one | 1000 | 50 | 50 | 0.8 |
| Example two | 1000 | 50 | 150 | 1.6 |
| EXAMPLE III | 1000 | 50 | 250 | 2.4 |
| Example four | 1000 | 50 | 350 | 3.2 |
| EXAMPLE five | 1000 | 50 | 450 | 4.0 |
The preparation method of the high impact resistance and high load bearing polypropylene composite material comprises the following steps:
firstly, carrying out surface modification treatment on a filler and a reinforcing fiber by adopting a silane coupling agent, wherein the surface modification method of the modified filler comprises the following steps: adding a silane coupling agent diluted by absolute ethyl alcohol into the talcum powder, wherein the adding amount of the silane coupling agent is 0.8-1% of the mass of the talcum powder, and the mass ratio of the absolute ethyl alcohol to the silane coupling agent is (9): 1, stirring and mixing uniformly in a high-speed mixer for 10 min; the surface modification method of the modified reinforced fiber comprises the following steps: adding a silane coupling agent diluted by absolute ethyl alcohol into wollastonite fibers, wherein the adding amount of the silane coupling agent is 0.8-1% of the mass of the wollastonite fibers, and the mass ratio of the absolute ethyl alcohol to the silane coupling agent is 9: 1, stirring and mixing uniformly in a high-speed mixer for 10 min. The raw materials were then weighed out according to the raw material composition described in example one.
And step two, blending the raw materials in a high-speed mixer for 5min to ensure that the polypropylene, the modified talcum powder and the modified wollastonite fiber are fully and uniformly mixed, then placing the mixed substance in an electrothermal vacuum drying oven, and drying for 2h at the drying temperature of 80 ℃ to obtain a mixed material.
And step three, extruding and granulating by adopting a double-screw extruder, wherein the temperature of each area of the double-screw extruder is set as follows: the temperature of a zone I is 80 ℃, the temperature of a zone II is 120 ℃, the temperature of a zone III is 160 ℃, the temperature of a zone IV is 180 ℃, the temperature of a zone V-IX is 200 ℃, after the temperature of the double-screw extruder is raised to the set temperature, the mixed material is added into the double-screw extruder, and is subjected to blending extrusion and granulation by a granulator, and then is dried for 2 hours under the condition that the drying temperature of an electric heating vacuum drying oven is 80 ℃, so as to obtain granules;
step four, injection molding, namely performing injection molding on the granules by using a plastic injection molding machine, wherein the temperature of each zone of the plastic injection molding machine is set as follows: the GB/T17037.1-1997 standard sample bar is obtained by injection molding at 210 ℃, 220 ℃ and 200 ℃, and the high impact-resistant and high load-bearing polypropylene composite material is obtained by placing for more than 24 hours at room temperature.
The preparation methods of the second, third, fourth and fifth embodiments are the same as the first embodiment.
Example six, mechanical properties testing.
A. And (3) tensile property testing, namely performing tensile property testing on the composite materials of the first to fifth embodiments, taking a single polypropylene material as a control group, preparing the composite materials and the control group into standard sample bars according to the GB/T1040.2-2006 standard, and setting the pull-up rate to be 50 mm/min. The tensile property test of the composite material is carried out on a microcomputer-controlled universal tensile testing machine, and the test can obtain the tensile strength and the elongation at break of the composite material, and the result is shown in table 4.
TABLE 4 tensile Strength (MPa) of composites of examples one through five and control
Referring to table 4, it can be seen from the average value of the tensile strength measurement data that, in the composite material prepared by adding different wollastonite fiber parts based on 5 parts of talc powder, the tensile strength of the second embodiment is only slightly improved, and is improved by 2.8% compared with the control group, the tensile strength of the composite material in other proportions is reduced compared with the control group, and the tensile strength of the composite material obtained under the condition of only adding the talc powder is improved, so that the tensile property of the composite material is inhibited after the wollastonite fiber is added.
B. Notch impact strength test, the composite materials of the first to fifth examples are subjected to notch impact strength test, a single polypropylene material is used as a control group, the composite material is firstly prepared into a standard sample strip according to the GB/T1043.1-2008 standard, the standard sample strip is prepared into a B-shaped notch by a notch sampling machine, the notch depth is 2mm, and the pendulum impact energy is 4J. The impact properties of the composites were tested on a pendulum impact tester to obtain notched impact strength for the composites, see table 5.
TABLE 5 notched Izod impact Strength (kJ/m) for composites of examples one through five and control2)
Referring to table 5, it can be seen from the average value of the notched impact strength measurement data that, in the composite material prepared by adding different wollastonite fiber parts based on 5 parts of talc powder, the notched impact strength increases first and then decreases, and the impact strength of the composite material of example two is the largest, which is improved by 4.2% compared with the control group, but the impact strength of the composite material is not significantly improved under the condition of only adding talc powder, so that the impact strength of the wollastonite fiber on the composite material is not greatly affected.
C. And (3) bending property testing, namely performing bending property testing on the composite materials of the first to fifth embodiments, taking a single polypropylene material as a comparison group, testing the bending strength of a sample according to GB/T9341-2008, wherein the specification of the sample is 84mm multiplied by 10mm multiplied by 4mm, the span is 64mm, the speed is 2mm/min, the deflection is 6mm, performing the bending property testing on the composite material on a microcomputer-controlled universal tensile testing machine, and obtaining the bending strength of the composite material through the testing, wherein the results are shown in Table 6.
TABLE 6 flexural Strength (MPa) of composites of examples one through five and control
Referring to table 6, it can be seen from the average value of the bending strength measurement data that the bending strength is greatly improved in the composite material prepared by adding different wollastonite fiber parts based on 5 talc powder parts, and the bending strength is increased along with the increase of the wollastonite fiber content.
Through a series of mechanical property tests on the composite material, after the talcum powder and the wollastonite fiber are added, the tensile strength and the impact strength of the composite material are not greatly influenced in most of proportions, and the tensile strength and the impact strength are improved only under the condition that the proportion of the talcum powder, the wollastonite fiber and the polypropylene is 5/15/100; the bending strength is the most important influence on the mechanical properties of the composite material by adding the talcum powder and the wollastonite fiber, and the bending strength is increased along with the increase of the content of the wollastonite fiber. The obtained composite material is used as a plastic tray, so that the bending strength of the material is improved on the premise of ensuring the original tensile strength and impact strength, and the plastic tray has the advantages of high bearing capacity, high toughness and low cost.
Example eight, scanning electron microscopy analysis was performed on the composites of example two and example three, respectively.
The cold brittle fracture surfaces obtained by cooling the composite materials of the second and third examples with liquid nitrogen and breaking the composite materials are observed under a JSM-6460LV type scanning electron microscope of Japan electronic Co., Ltd, the structural appearance of the fracture surfaces, the difference of morphological structures presented in the microcosmic state and the dispersion state of the filler in the polypropylene resin are observed, and because all components forming the composite materials are not conductive, before the composite materials are observed under the scanning electron microscope, a sample is subjected to gold plating treatment to enable the surface of the composite materials to have conductivity, and then the fracture surfaces of the composite materials are scanned under the electron microscope, so that SEM images of the composite materials under different formulas are obtained, and the results are shown in figures 1 to 4.
Referring to fig. 1 to 4, the cross sections of the composite material under different proportions are rough, a large number of flaky structures talc with consistent orientation can be seen in the cross sections, the orientations of the talcum powder and the wollastonite fibers are consistent, and broken wollastonite fibers are more than pulled wollastonite fibers in the pictures, which means that the cohesive failure between the wollastonite fibers and the matrix is reduced, and the wollastonite fibers bear more internal stress, so that the bending performance of the composite material is improved, and the observation result is consistent with the previous mechanical property test result.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. A high impact-resistant high-bearing polypropylene composite material is characterized in that: is prepared from a raw material composition comprising: 100 parts by weight of polypropylene, 5-20 parts by weight of modified filler and 5-45 parts by weight of modified reinforcing fiber;
the modified filler and the modified reinforcing fiber are both subjected to surface modification treatment by adopting a silane coupling agent.
2. The high impact, high load bearing polypropylene composite of claim 1, wherein: the raw material composition comprises: 100 parts by weight of polypropylene, 5 parts by weight of modified filler and 15 parts by weight of modified reinforcing fiber.
3. The high impact, high load bearing polypropylene composite according to claim 1 or 2, characterized in that: the surface modification method of the modified filler comprises the following steps: adding a silane coupling agent diluted by absolute ethyl alcohol into a filling agent, wherein the adding amount of the silane coupling agent is 0.8-1% of the mass of the filling agent, and the mass ratio of the absolute ethyl alcohol to the silane coupling agent is (9): 1, stirring and mixing uniformly in a high-speed mixer for 5-30 min; the filler is superfine talcum powder, nano calcium carbonate, mica powder or nano clay.
4. The high impact, high load bearing polypropylene composite according to claim 1 or 2, characterized in that: the surface modification method of the modified reinforced fiber comprises the following steps: adding a silane coupling agent diluted by absolute ethyl alcohol into the reinforced fiber, wherein the adding amount of the silane coupling agent is 0.8-1% of the mass of the reinforced fiber, and the mass ratio of the absolute ethyl alcohol to the silane coupling agent is 9: 1, stirring and mixing uniformly in a high-speed mixer for 5-30 min, wherein the reinforcing fiber is wollastonite fiber, basalt short fiber or chopped carbon fiber.
5. A preparation method of a high impact resistance and high bearing polypropylene composite material is characterized by comprising the following steps:
firstly, carrying out surface modification treatment on a filler and a reinforcing fiber by using a silane coupling agent, and then weighing raw materials according to the raw material composition of any one of claims 1-5;
blending the raw materials in a high-speed mixer for 1-5 min, and drying to obtain a mixed material;
and step three, extruding and granulating by using a double-screw extruder to obtain granules, wherein the temperature of each area of the double-screw extruder is set as follows: the temperature of the first area is 70-90 ℃, the temperature of the second area is 110-130 ℃, the temperature of the third area is 150-170 ℃, the temperature of the fourth area is 170-190 ℃, and the temperature of the fifth-IX area is 190-210 ℃;
step four, injection molding, namely performing injection molding on the granules by using an injection molding machine to obtain the high-impact-resistance and high-bearing polypropylene composite material, wherein the temperature of each zone of the injection molding machine is set as follows: 200 to 220 ℃, 210 to 230 ℃ and 190 to 210 ℃.
6. Use of the high impact, high load polypropylene composite of any one of claims 1 to 4 or the high impact, high load polypropylene composite produced according to claim 5 as a plastic pallet.
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