CN115572455A - Phosphogypsum whisker/fiber reinforced composite material and preparation method thereof - Google Patents
Phosphogypsum whisker/fiber reinforced composite material and preparation method thereof Download PDFInfo
- Publication number
- CN115572455A CN115572455A CN202211373130.0A CN202211373130A CN115572455A CN 115572455 A CN115572455 A CN 115572455A CN 202211373130 A CN202211373130 A CN 202211373130A CN 115572455 A CN115572455 A CN 115572455A
- Authority
- CN
- China
- Prior art keywords
- composite material
- phosphogypsum
- parts
- fiber
- whisker
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 title claims abstract description 74
- 239000000463 material Substances 0.000 title claims abstract description 27
- 239000003733 fiber-reinforced composite Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 41
- 239000000835 fiber Substances 0.000 claims abstract description 36
- 239000002131 composite material Substances 0.000 claims abstract description 26
- 239000011159 matrix material Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920006253 high performance fiber Polymers 0.000 claims abstract description 16
- 239000012745 toughening agent Substances 0.000 claims abstract description 16
- 230000008014 freezing Effects 0.000 claims abstract description 15
- 238000007710 freezing Methods 0.000 claims abstract description 15
- 239000008187 granular material Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000000748 compression moulding Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 12
- 239000004917 carbon fiber Substances 0.000 claims description 12
- 229920002943 EPDM rubber Polymers 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229920001973 fluoroelastomer Polymers 0.000 claims description 7
- 229920002748 Basalt fiber Polymers 0.000 claims description 6
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical group [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 5
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- NRCSJPUCBTUPDG-UHFFFAOYSA-N benzyl-chloro-triphenyl-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(Cl)(C=1C=CC=CC=1)CC1=CC=CC=C1 NRCSJPUCBTUPDG-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- -1 benzyl triphenyl phosphorus chloride Chemical compound 0.000 claims description 2
- 238000010494 dissociation reaction Methods 0.000 claims description 2
- 230000005593 dissociations Effects 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 239000009719 polyimide resin Substances 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 9
- 239000006185 dispersion Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000007906 compression Methods 0.000 description 15
- 230000006835 compression Effects 0.000 description 15
- 244000226021 Anacardium occidentale Species 0.000 description 6
- 235000020226 cashew nut Nutrition 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000010466 nut oil Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- VNWKTOKETHGBQD-YPZZEJLDSA-N carbane Chemical group [10CH4] VNWKTOKETHGBQD-YPZZEJLDSA-N 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/14—Modified phenol-aldehyde condensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use 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; Derivatives of such polymers
- C08J2427/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a phosphogypsum whisker/fiber reinforced composite material and a preparation method thereof, wherein the composite material consists of 5-30 parts of a resin matrix, 1-20 parts of a toughening agent, 5-40 parts of phosphogypsum whisker, 1-30 parts of high-performance fiber, 5-80 parts of a filler and 0.1-4 parts of a vulcanizing agent, and during preparation, the fiber is firstly uniformly dissociated and then is mixed with the resin matrix, the phosphogypsum whisker and the filler to obtain a velvet mixture; secondly, uniformly mixing the toughening agent, the phosphogypsum whiskers, the high-performance fibers and the vulcanizing agent, granulating in a torque rheometer and a single-screw extruder unit, and grinding the granules into powdery particles in a freezing pulverizer; and finally, uniformly mixing the obtained fluffy mixture and the powdery particles in a V-shaped mixer, and carrying out compression molding to obtain the composite material. The composite material prepared by the invention has the advantages of high friction coefficient, low wear rate, high mechanical strength, uniform dispersion of the fiber and the phosphogypsum whisker and high length retention rate, and is particularly suitable for industrial production.
Description
Technical Field
The invention relates to an ardealite whisker/fiber reinforced composite material and a preparation method thereof, in particular to an ardealite whisker and high-performance chopped fiber synergistically reinforced resin-based composite material and a preparation method thereof, belonging to the technical field of composite materials.
Background
In recent years, as phosphogypsum waste materials are accumulated like a mountain, the storage problem of phosphogypsum becomes a difficult problem, the development of phosphorite is seriously influenced, the environmental hazard is extremely large, the comprehensive utilization of the phosphogypsum is at hand, and further, the research on the remanufacturing and modification of the phosphogypsum is promoted by nearly 30 scientific research institutions and enterprises in China, the synthesis of phosphogypsum whiskers (the main component is calcium sulfate) is one of the main ways of recycling the phosphogypsum, the phosphogypsum whiskers are applied to the composite material industry, and the utilization problem of the phosphogypsum is greatly solved.
The inorganic calcium salt whisker is widely applied to composite materials due to good chemical stability, high heat resistance, excellent wear resistance and mechanical property, lower price and higher cost performance, wherein the phosphogypsum whisker prepared by taking solid waste phosphogypsum generated in phosphoric acid production as a raw material has the advantages of good toughness, high strength, high temperature resistance, no toxicity and the like, and can provide more stable friction coefficient, wear resistance, heat resistance and mechanical property and prolong the service life of the material when being cooperatively applied to the composite materials with high-performance fibers.
In view of this, it is important to research a phosphogypsum whisker/fiber reinforced composite material.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the phosphogypsum whisker/fiber reinforced composite material and the preparation method thereof are provided, the phosphogypsum whisker and chopped fiber synergistic reinforced resin matrix composite material is prepared by a three-step method, and the obtained composite material has the advantages of uniform distribution of phosphogypsum whiskers and fibers, high length retention rate and high and stable mechanical and frictional properties, so that the defects of the prior art are overcome.
The technical scheme adopted by the invention for solving the technical problems is as follows: the phosphogypsum whisker/fiber reinforced composite material comprises, by weight, 5-30 parts of a resin matrix, 1-20 parts of a toughening agent, 5-40 parts of phosphogypsum whiskers, 1-30 parts of high-performance fibers, 5-80 parts of a filler and 0.1-4 parts of a vulcanizing agent. The adoption of the SHR high-speed mixer not only can uniformly mix the defibered fiber, the phosphogypsum whisker, the powdery resin matrix and the filler, but also can improve the length retention rate of the fiber and the phosphogypsum whisker in the mixing process. In the scheme, the toughening agent is mainly used for improving the toughness and the compression elasticity of the composite material, so that the impact resistance and the actual contact area of the composite material in the friction braking process are improved, and the friction performance is improved.
Preferably, the toughening agent is one or two of fluororubber or Ethylene Propylene Diene Monomer (EPDM). Fluororubber and EPDM are elastomers with good heat resistance, weather resistance, ozone resistance, oil resistance and chemical resistance, and can provide toughness and viscoelasticity for the composite material, and improve the impact strength of the composite material and the actual contact area in the friction process. However, excessive amounts of fluororubber and EPDM may reduce the shear strength and tensile strength of the composite and the adhesion to the resin matrix, affecting the overall properties of the composite.
Preferably, the main component of the phosphogypsum whisker is calcium sulfate, the length is 10-500 mu m, and the length-diameter ratio is 10-200. The phosphogypsum whisker adopted in the invention is a phosphogypsum whisker subjected to surface treatment by a silane coupling agent or a rare earth coupling agent, and the bonding property between the phosphogypsum whisker and a resin matrix and between the phosphogypsum whisker and a rubber toughening agent is improved.
Preferably, the resin matrix is one or two of powdered cashew nut oil modified phenolic resin, boron modified phenolic resin or polyimide resin, and the granularity is 30-1000 meshes. The cashew nut oil modified phenolic resin and the boron phenolic resin have high heat resistance, instantaneous high temperature resistance and excellent mechanical property, the polyimide is a thermosetting resin with high temperature resistance of 400 ℃ and excellent mechanical property, and two resin matrixes can improve the initial thermal decomposition temperature and the overall heat resistance of the composite material, and are favorable for improving the heat fading resistance and the friction stability of the composite material in the friction braking process.
Preferably, the high-performance fiber is one or more of chopped carbon fiber, graphite fiber, basalt fiber or aramid fiber, the length is 0.01-6mm, and the length-diameter ratio is 1:1-1000. The high-performance fibers with different lengths can form a bridging effect, so that the composite material is reinforced in a three-dimensional multi-scale space, the isotropy degree of the composite material is improved, and the mechanical strength and the heat resistance are improved.
Preferably, the filler is one or more of alumina, calcium carbonate, barium sulfate, graphite, magnesium oxide and zinc oxide.
Preferably, the vulcanizing agent is one of a bisphenol AF/benzyltriphenylphosphonium chloride system or a dicumyl peroxide/triallyl isocyanurate system, the mass ratio of the bisphenol AF to the benzyltriphenylphosphonium chloride system is 1-10.
The preparation method of the phosphogypsum whisker/fiber reinforced composite material comprises the following steps:
(1) Uniformly dissociating the metered high-performance fibers in a fiber fluffer at the rotating speed of 1000-3000r/min, and uniformly mixing the high-performance fibers with the metered resin matrix, the phosphogypsum whiskers and the fillers in an SHR high-speed mixer to obtain a fluffy mixture, wherein the charging barrel temperature is 15-50 ℃, and the mixing rotating speed is 1000-3000r/min; the good dissociation capability of the defibrator on the fiber is utilized in the step to improve the dispersibility of the fiber protofilament, the phenomenon of uneven dispersion when the fasciculate fiber is directly added in the mixing process is avoided, meanwhile, the full dispersion of the fiber protofilament can be ensured and the fiber protofilament can be prevented from being broken in the temperature and rotating speed range, the length retention rate of the fiber is ensured, and the reinforcing effect of the fiber in the composite material is fully exerted; in the step, the SHR high-speed mixer is utilized to uniformly mix the fibers, the resin matrix, the phosphogypsum whiskers and the filler within the temperature and rotating speed range, the fibers and the phosphogypsum whiskers can be prevented from being broken, the overhigh temperature rise caused by heat generation due to friction in the mixing process can be reduced, and the resin matrix is prevented from being cured or decomposed in advance.
(2) Uniformly mixing the measured flexibilizer, the phosphogypsum whiskers, the high-performance fibers and the vulcanizing agent in a high-speed mixer, granulating in a torque rheometer and a single-screw extruder unit, wherein the temperature of a charging barrel is 150-250 ℃, the mixing rotating speed is 50-200r/min, grinding the granules into powdery particles by a freezing pulverizer, the freezing temperature is 0-196 ℃, and the rotating speed is 1000-6000r/min; in the step, the good mixing capability of a torque rheometer and a single-screw extruder unit is utilized to improve the dispersibility of the phosphogypsum whiskers and high-performance fibers in the toughening agent, and meanwhile, the length retention rate of the phosphogypsum whiskers and the fibers is ensured by utilizing lower shearing force, so that the mixture of the toughening agent, the phosphogypsum and the fibers can be easily processed and uniformly mixed in the temperature and rotating speed range, and the phosphogypsum whiskers and the fibers can be prevented from being seriously cracked; in the step, the uniform crushing of the toughening agent granules can be realized by using a freezing pulverizer at the temperature and the rotating speed, and the phosphogypsum whiskers and fibers have high length retention rate.
(3) And (3) uniformly mixing the velvet-shaped mixture obtained in the steps (1) and (2) and the powdery particles in a V-shaped mixer, wherein the rotating speed of a cylinder body is 10-100r/min, the mixing time is 5-30min, so as to obtain a molding compound with uniformly dispersed components, and then carrying out compression molding to obtain the phosphogypsum whisker/fiber reinforced composite material, wherein the compression molding pressing temperature is 150-180 ℃, the compression pressure is 150-250 ℃, and the compression time is 5-20min. In the step, the velvet-shaped mixture and the powdery particles obtained in the steps (1) and (2) are mixed within the temperature and rotating speed range by utilizing the lower shearing force and the efficient mixing capacity of the V-shaped mixer, so that the mixture is easy to process and uniform in dispersion, and the phosphogypsum whiskers and fibers are not seriously broken in the processing process, so that the length retention rate of the fibers is improved, and the molding compound with stable performance is obtained; in the step, under the mould pressing temperature, pressure and time, the composite material is fully cured and formed, and the energy consumption is reduced. After the steps (1), (2) and (3), the problem of dispersibility of the fibers and the phosphogypsum whiskers in the resin matrix and the toughening agent is solved, the fibers and the phosphogypsum whiskers are prevented from being seriously broken in the processing process, meanwhile, the problems of low mechanical strength and bonding property with the resin matrix of the toughening agent are solved, and the comprehensive performance of the composite material is ensured.
The invention has the beneficial effects that: the invention provides a composite material which takes phosphogypsum whiskers or/and high-performance fibers as a reinforcement, modified phenolic resin or/and polyimide as a matrix and fluororubber or/and EPDM as a toughening agent, and can be applied to the fields of composite materials and friction braking materials. The phosphogypsum whisker and fiber in the composite material prepared by the method are uniformly dispersed, the length retention rate is high, the compatibility of the resin matrix and the toughening agent is high, and the mechanical strength and the friction performance are high.
Drawings
FIG. 1 is a shear cross-sectional view of example 1;
FIG. 2 is a shear cross-sectional view of example 2;
FIG. 3 is a shear sectional view of example 3;
FIG. 4 is a cut sectional view of example 4.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1:
(1) Firstly, uniformly dissociating 2.5 parts of carbon fiber and 7.5 parts of basalt fiber in a fiber fluffer at the rotating speed of 2000r/min, and then uniformly mixing the carbon fiber and 24.85 parts of cashew nut oil modified phenolic resin matrix, 10 parts of phosphogypsum whisker, 22.5 parts of calcium carbonate, 5 parts of graphite and 5 parts of alumina in an SHR high-speed mixer to obtain a fluffy mixture, wherein the charging barrel temperature is 25 ℃, and the mixing rotating speed is 1500r/min;
(2) 5 parts of EPDM (ethylene-propylene-diene monomer), 10 parts of phosphogypsum whisker, 7.5 parts of basalt fiber, 0.05 part of dicumyl peroxide and 0.1 part of triallyl isocyanurate system are uniformly mixed in a high-speed mixer, then the mixture is granulated in a torque rheometer and single-screw extruder unit, the temperature of a charging barrel is 150-180 ℃, the mixing speed is 100r/min, a freezing pulverizer is adopted to grind the granules into powdery granules, the freezing temperature is-150 ℃, and the rotating speed is 1500r/min;
(3) Uniformly mixing the velvet mixture and the powdery particles obtained in the steps (1) and (2) in a V-shaped mixer, wherein the rotating speed of a cylinder is 50r/min, the mixing time is 20min, obtaining a molding compound with uniformly dispersed components, then carrying out compression molding to obtain the phosphogypsum whisker/fiber reinforced composite material, wherein the compression temperature is 170 ℃, the compression pressure is 10MPa, and the compression time is 10min. The results of the performance test are shown in Table 1, and the cut surfaces are shown in FIG. 1.
Example 2:
(1) Firstly, 1.5 parts of carbon fiber and 10 parts of basalt fiber are uniformly dissociated in a fiber fluffer at the rotating speed of 2500r/min, and then are uniformly mixed with 19.7 parts of cashew nut oil modified phenolic resin matrix, 5 parts of phosphogypsum whisker, 22.5 parts of calcium carbonate, 5 parts of graphite and 5 parts of alumina in an SHR high-speed mixer to obtain a fluffy mixture, wherein the charging barrel temperature is 25 ℃, and the mixing rotating speed is 1500r/min;
(2) Uniformly mixing 10 parts of EPDM (ethylene-propylene-diene monomer), 15 parts of phosphogypsum whisker, 1 part of carbon fiber, 5 parts of basalt fiber, 0.1 part of dicumyl peroxide and 0.2 part of triallyl isocyanurate system in a high-speed mixer, granulating in a torque rheometer and single-screw extruder unit, wherein the temperature of a charging barrel is 150-180 ℃, the mixing speed is 150r/min, grinding the granules into powdery granules by adopting a freezing pulverizer, and the freezing temperature is-196 ℃ and the rotating speed is 2000r/min;
(3) Uniformly mixing the velvet-shaped mixture obtained in the steps (1) and (2) and the powdery particles in a V-shaped mixer, wherein the rotating speed of a cylinder body is 45r/min, the mixing time is 30min, obtaining a molding compound with uniformly dispersed components, and then carrying out compression molding to obtain the phosphogypsum whisker/fiber reinforced composite material, wherein the compression temperature is 170-180 ℃, the compression pressure is 15MPa, and the compression time is 10min. The results of the performance test are shown in Table 1, and the shear cross section is shown in FIG. 2.
Example 3:
(1) Firstly, uniformly dissociating 4 parts of carbon fiber in a fiber fluffer at the rotating speed of 3000r/min, and then uniformly mixing the carbon fiber with 19.87 parts of cashew nut oil modified phenolic resin matrix, 15 parts of phosphogypsum whisker, 20 parts of calcium carbonate, 20 parts of barium sulfate, 5 parts of graphite and 5 parts of aluminum oxide in an SHR high-speed mixer to obtain a fluffy mixture, wherein the charging barrel temperature is 35 ℃, and the mixing rotating speed is 2500r/min;
(2) Uniformly mixing 5 parts of fluororubber, 5 parts of phosphogypsum whiskers, 1 part of carbon fibers, 0.11 part of bisphenol AF and 0.02 part of benzyl triphenyl phosphorus chloride system in a high-speed mixer, granulating in a torque rheometer and a single-screw extruder unit, wherein the temperature of a charging barrel is 160-200 ℃, the mixing rotating speed is 120r/min, and grinding the granules into powdery granules by adopting a freezing pulverizer, wherein the freezing temperature is-150 ℃, and the rotating speed is 2000r/min;
(3) Uniformly mixing the velvet-shaped mixture and the powdery particles obtained in the steps (1) and (2) in a V-shaped mixer, wherein the rotating speed of a cylinder body is 60r/min, the mixing time is 30min, obtaining a molding compound with uniformly dispersed components, and then carrying out compression molding to obtain the phosphogypsum whisker/fiber reinforced composite material, wherein the compression temperature is 170-180 ℃, the compression pressure is 10MPa, and the compression time is 10min. The results of the performance test are shown in Table 1, and the cut surfaces are shown in FIG. 3.
Example 4:
(1) Firstly, uniformly dissociating 2.5 parts of carbon fiber in a fiber fluffer at the rotating speed of 2000r/min, and then uniformly mixing the carbon fiber with 19.75 parts of cashew nut oil modified phenolic resin matrix, 10 parts of phosphogypsum whisker, 15 parts of calcium carbonate, 20 parts of barium sulfate, 5 parts of graphite and 5 parts of aluminum oxide in an SHR high-speed mixer to obtain a fluffy mixture, wherein the charging barrel temperature is 40 ℃, and the mixing rotating speed is 2000r/min;
(2) Uniformly mixing 10 parts of fluororubber, 10 parts of phosphogypsum whiskers, 2.5 parts of carbon fibers, 0.21 part of bisphenol AF and 0.04 part of benzyl triphenyl phosphorus chloride system in a high-speed mixer, granulating in a torque rheometer and single-screw extruder set, wherein the temperature of a charging barrel is 160-200 ℃, the mixing rotating speed is 200r/min, grinding the granules into powdery granules by adopting a freezing pulverizer, and the freezing temperature is-196 ℃ and the rotating speed is 2500r/min;
(3) Uniformly mixing the velvet-shaped mixture obtained in the steps (1) and (2) and the powdery particles in a V-shaped mixer, wherein the rotating speed of a cylinder body is 55r/min, the mixing time is 25min, obtaining a molding compound with uniformly dispersed components, and then carrying out compression molding to obtain the phosphogypsum whisker/fiber reinforced composite material, wherein the compression temperature is 170-180 ℃, the compression pressure is 15MPa, and the compression time is 15min. The results of the performance test are shown in Table 1, and the cut surfaces are shown in FIG. 4.
TABLE 1
As can be seen from the table 1 and the figures 1 to 4, the phosphogypsum whisker/fiber reinforced composite material has the advantages of high friction coefficient, low wear rate, high shear strength and impact strength, uniform dispersion of the fiber and the phosphogypsum whisker and high retention rate of the length of the fiber.
In addition, the end of the range provided by the formulations of the present invention is parallel to the values in examples 1-4 above, and therefore will not be repeated.
The above-mentioned embodiments are only one embodiment of the present invention, and not all or only one embodiment, and any equivalent changes to the technical solutions of the present invention by a person of ordinary skill in the art through reading the specification are within the protection scope of the present invention.
Claims (9)
1. A preparation method of a phosphogypsum whisker/fiber reinforced composite material is characterized by comprising the following steps: the composite material comprises, by weight, 5-30 parts of a resin matrix, 1-20 parts of a toughening agent, 5-40 parts of phosphogypsum whiskers, 1-30 parts of high-performance fibers, 5-80 parts of a filler and 0.1-4 parts of a vulcanizing agent, wherein the toughening agent is one or two of fluororubber or Ethylene Propylene Diene Monomer (EPDM), and the preparation method comprises the following steps:
(1) Uniformly dissociating the metered high-performance fibers in a fiber fluffer, and uniformly mixing the high-performance fibers with the metered resin matrix, the phosphogypsum whiskers and the fillers in an SHR high-speed mixer to obtain a fluffy mixture;
(2) Uniformly mixing a toughening agent, phosphogypsum whiskers, high-performance fibers and a vulcanizing agent in a high-speed mixer, granulating in a torque rheometer and a single-screw extruder unit, and grinding the granules into powdery particles by using a freezing pulverizer;
(3) And (3) uniformly mixing the velvet-shaped mixture obtained in the steps (1) and (2) and the powdery particles in a V-shaped mixer, and performing compression molding to obtain the phosphogypsum whisker/fiber reinforced composite material.
2. The method for preparing the phosphogypsum whisker/fiber reinforced composite material according to claim 1, which is characterized in that: the main component of the phosphogypsum whisker is calcium sulfate, the length is 10-500 mu m, and the length-diameter ratio is 10-200.
3. The method for preparing the phosphogypsum whisker/fiber reinforced composite material according to claim 1, which is characterized in that: the resin matrix is one or two of powdered modified thermosetting phenolic resin or polyimide resin, and the granularity is 30-1000 meshes.
4. The method for preparing the phosphogypsum whisker/fiber reinforced composite material according to claim 1, wherein the method comprises the following steps: the vulcanizing agent is one of a bisphenol AF/benzyl triphenyl phosphorus chloride system or a dicumyl peroxide/triallyl isocyanurate system, the mass ratio of the bisphenol AF to the benzyl triphenyl phosphorus chloride system is 1-10.
5. The method for preparing the phosphogypsum whisker/fiber reinforced composite material according to claim 1, which is characterized in that: the high-performance fiber is one or more of carbon fiber, graphite fiber, basalt fiber or aramid fiber, the length is 0.01-6mm, and the length-diameter ratio is 1:1-1000.
6. The method for preparing the phosphogypsum whisker/fiber reinforced composite material according to claim 1, which is characterized in that: the filler is one or more of aluminum oxide, calcium carbonate, barium sulfate, graphite, magnesium oxide and zinc oxide.
7. The method for preparing the phosphogypsum whisker/fiber reinforced composite material according to claim 1, which is characterized in that: in the step (1), the dissociation rotating speed of the fiber fluffer is 1000-3000r/min, the temperature of a charging barrel of the mixer is 25-50 ℃, and the mixing rotating speed is 1000-3000r/min.
8. The method for preparing the phosphogypsum whisker/fiber reinforced composite material according to claim 1, which is characterized in that: in the step (2), the temperature of a charging barrel of the extruder unit is 150-250 ℃, the mixing speed is 50-200r/min, the freezing temperature of the freezing pulverizer is 0-196 ℃, and the grinding speed is 1000-6000r/min.
9. The method for preparing the phosphogypsum whisker/fiber reinforced composite material according to claim 1, which is characterized in that: in the step (3), the rotating speed of the cylinder of the V-shaped mixer is 10-100r/min, the mixing time is 5-30min, the mould pressing temperature is 150-180 ℃, the pressing pressure is 150-250 ℃, and the pressing time is 5-20min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211373130.0A CN115572455A (en) | 2022-11-04 | 2022-11-04 | Phosphogypsum whisker/fiber reinforced composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211373130.0A CN115572455A (en) | 2022-11-04 | 2022-11-04 | Phosphogypsum whisker/fiber reinforced composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115572455A true CN115572455A (en) | 2023-01-06 |
Family
ID=84589651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211373130.0A Pending CN115572455A (en) | 2022-11-04 | 2022-11-04 | Phosphogypsum whisker/fiber reinforced composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115572455A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117264414A (en) * | 2023-10-17 | 2023-12-22 | 南京长澄科技制造有限公司 | High-temperature-resistant wear-resistant anti-cracking friction plate and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4994506A (en) * | 1989-08-31 | 1991-02-19 | Redco N.V. | Brake linings |
| CN102925105A (en) * | 2012-10-10 | 2013-02-13 | 西北工业大学 | Calcium-sulfate-whisker-reinforced carbon fiber resin-base friction material and preparation method thereof |
| CN102965078A (en) * | 2012-11-23 | 2013-03-13 | 山东金麒麟股份有限公司 | Friction material of disc brake pad, disc brake pad and preparation technology of disc brake pad |
| CN103436236A (en) * | 2013-08-28 | 2013-12-11 | 李美凤 | Palm fiber-reinforced environment-friendly type brake pad and preparation method thereof |
| CN104531070A (en) * | 2014-12-29 | 2015-04-22 | 西北工业大学 | Softwood particle blending and modified rubber based friction material as well as preparation method and using method thereof |
| CN105111675A (en) * | 2015-08-06 | 2015-12-02 | 广西碳酸钙产业化工程院有限公司 | Calcium carbonate whisker reinforced resin-rubber base friction material and preparation method therefor |
| CN105546000A (en) * | 2015-12-31 | 2016-05-04 | 江苏贝事特汽车配件有限公司 | High-strength and high-tenacity brake pad |
| CN113882021A (en) * | 2021-10-12 | 2022-01-04 | 贵州大学 | Method for preparing calcium sulfate whisker by phosphogypsum high-temperature high-pressure method |
-
2022
- 2022-11-04 CN CN202211373130.0A patent/CN115572455A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4994506A (en) * | 1989-08-31 | 1991-02-19 | Redco N.V. | Brake linings |
| CN102925105A (en) * | 2012-10-10 | 2013-02-13 | 西北工业大学 | Calcium-sulfate-whisker-reinforced carbon fiber resin-base friction material and preparation method thereof |
| CN102965078A (en) * | 2012-11-23 | 2013-03-13 | 山东金麒麟股份有限公司 | Friction material of disc brake pad, disc brake pad and preparation technology of disc brake pad |
| CN103436236A (en) * | 2013-08-28 | 2013-12-11 | 李美凤 | Palm fiber-reinforced environment-friendly type brake pad and preparation method thereof |
| CN104531070A (en) * | 2014-12-29 | 2015-04-22 | 西北工业大学 | Softwood particle blending and modified rubber based friction material as well as preparation method and using method thereof |
| CN105111675A (en) * | 2015-08-06 | 2015-12-02 | 广西碳酸钙产业化工程院有限公司 | Calcium carbonate whisker reinforced resin-rubber base friction material and preparation method therefor |
| CN105546000A (en) * | 2015-12-31 | 2016-05-04 | 江苏贝事特汽车配件有限公司 | High-strength and high-tenacity brake pad |
| CN113882021A (en) * | 2021-10-12 | 2022-01-04 | 贵州大学 | Method for preparing calcium sulfate whisker by phosphogypsum high-temperature high-pressure method |
Non-Patent Citations (1)
| Title |
|---|
| 陈辉 等: ""硫酸钙晶须增强树脂基复合摩擦材料摩擦磨损性能的研究"", 《化工新型材料》, vol. 40, no. 8, pages 111 - 112 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117264414A (en) * | 2023-10-17 | 2023-12-22 | 南京长澄科技制造有限公司 | High-temperature-resistant wear-resistant anti-cracking friction plate and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sullins et al. | Hemp fiber reinforced polypropylene composites: The effects of material treatments | |
| CN104405807B (en) | A kind of preparation method of automobile brake sheet | |
| CN103333406B (en) | A kind of modified expanded flame-proof polypropelene composition and preparation method thereof | |
| CN115572455A (en) | Phosphogypsum whisker/fiber reinforced composite material and preparation method thereof | |
| CN102952309B (en) | Improved short carbon fiber reinforced polyolefin composite material and preparation method thereof | |
| CN105111675B (en) | A kind of calcium carbonate crystal whisker reinforced resin-Rubber base friction material and preparation method thereof | |
| CN102260406A (en) | Methyl cellulose (MC) nylon nano conductive composite material and preparation method thereof | |
| CN112228483B (en) | Modified organic filling material for friction material and preparation process thereof | |
| CN101081922A (en) | Phenolic plastic and preparation technique thereof | |
| CN101077912A (en) | Asbestos-free non-metal friction material and preparation method thereof | |
| CN110818990A (en) | Preparation method of light slow-running shoe sole | |
| CN111171513B (en) | Method for toughening thermosetting resin by using collagen fibers and modified thermosetting resin | |
| CN113388173B (en) | Synthetic friction material and preparation method and application thereof | |
| CN110482893A (en) | A kind of anti-cracking plastering mortar and preparation method thereof | |
| CN105972132B (en) | A kind of wingceltis fiber reinforcement environment-friendly type brake block | |
| CN112324826A (en) | Comfortable high-temperature-resistant brake pad | |
| CN115558213A (en) | Low-dielectric high-thermal-conductivity high-strength composite film and preparation method thereof | |
| CN115160606A (en) | Composite material with high tensile strength and impact strength and preparation method thereof | |
| CN101696288B (en) | Preparation method of scrap rubber powder-hard rubber composite reinforced by waste fibers from rubber reclaiming | |
| CN107337833A (en) | A kind of preparation method for mixing plastic-wood floor material | |
| CN106188747A (en) | A kind of environmental protection flame retardant foamed materials and preparation method thereof | |
| CN110760124B (en) | Glass fiber waste silk reinforced polypropylene composite material and preparation method thereof | |
| CN106633846A (en) | Plastic electric power fitting composite material with high high-temperature resistance strength and manufacturing method thereof | |
| CN110066455B (en) | Abrasion-resistant antistatic polypropylene material and preparation method thereof | |
| CN102221058A (en) | Asbestos-free inorfil friction plate and manufacturing technology thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20230106 |
|
| WD01 | Invention patent application deemed withdrawn after publication |