CN117088360A - Preparation method of nano porous carbon additive for rubber engineering equipment - Google Patents
Preparation method of nano porous carbon additive for rubber engineering equipment Download PDFInfo
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- CN117088360A CN117088360A CN202311352774.6A CN202311352774A CN117088360A CN 117088360 A CN117088360 A CN 117088360A CN 202311352774 A CN202311352774 A CN 202311352774A CN 117088360 A CN117088360 A CN 117088360A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 65
- 239000000654 additive Substances 0.000 title claims abstract description 64
- 230000000996 additive effect Effects 0.000 title claims abstract description 63
- 229920001971 elastomer Polymers 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000000498 ball milling Methods 0.000 claims abstract description 121
- 239000000463 material Substances 0.000 claims abstract description 90
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 27
- 239000004917 carbon fiber Substances 0.000 claims abstract description 27
- 239000006185 dispersion Substances 0.000 claims abstract description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920001661 Chitosan Polymers 0.000 claims abstract description 16
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 15
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 12
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 239000011324 bead Substances 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 14
- 238000003763 carbonization Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 8
- 238000012360 testing method Methods 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 20
- 239000011148 porous material Substances 0.000 description 13
- 230000001681 protective effect Effects 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002354 daily effect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- -1 polyoxyethylene octyl phenol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012791 sliding layer Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention relates to a preparation method of a nano porous carbon additive for rubber engineering equipment, which comprises the following steps: A. adding 4-6g of silicon carbide into 230-270ml of deionized water, and then performing ultrasonic dispersion to obtain a dispersion liquid; adding 15-25g of chitosan, 15-25ml of 65-75wt% phytic acid solution, 8-12ml of OP-10 and 1.5-2.5g of nano carbon fiber into the dispersion liquid to obtain a ball abrasive; B. ball milling is carried out on ball grinding materials, ball milling balls are taken out after ball milling is finished, and the ball milling materials are frozen and dried to obtain gel-like materials; C. carbonizing the gel material at 850-950 ℃ in inert gas atmosphere to obtain the nano porous carbon additive. The carbon material prepared by the method can effectively reinforce rubber and enhance the wear resistance of the rubber.
Description
Technical Field
The invention relates to a preparation method of a nano porous carbon additive for rubber engineering equipment, belonging to the technical field of carbon materials.
Background
Carbon is one of the most common elements in natural distribution, and single bonds are formed by sp3 hybridization among atoms, and stable double bonds and triple bonds can be formed by sp3 and sp hybridization, so that allotropes with very different structures and properties, such as zero-dimensional carbon black and fullerene, one-dimensional carbon nanotubes and carbon nanofibers, two-dimensional graphene and the like, can be formed. From traditional carbon black to latest two-dimensional graphene, carbon materials have been widely applied to the fields of adsorbents, catalysts, fuel cells, electrode materials of secondary batteries, supercapacitors, composite materials, gas sensors, solar cells, various electronic devices and the like by virtue of unique and excellent mechanical, electrical, thermal and other properties.
The carbon material can be used as a filler to be added into rubber, can enhance the physical, thermal, electrical and gas/liquid barrier properties of the rubber, and can reduce the production cost of rubber products. At present, carbon materials commonly used in rubber are graphite, carbon black, graphene oxide, carbon fiber and carbon nano tube, but the carbon materials have a plurality of defects, and cannot fully exert the reinforcing effect, such as easy agglomeration in a rubber matrix and difficult good combination with the rubber matrix.
Therefore, it is very necessary to develop a carbon material having a good reinforcing effect.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a nano porous carbon additive capable of effectively reinforcing the mechanical property of rubber, and provides a preparation method and application thereof in rubber.
In order to solve the problems, the invention adopts the following technical scheme:
subject 1
The preparation method of the nano porous carbon additive for the rubber engineering equipment comprises the following steps:
A. adding 4-6g of silicon carbide into 230-270ml of deionized water, and then performing ultrasonic dispersion to obtain a dispersion liquid; adding 15-25g of chitosan, 15-25ml of 65-75wt% phytic acid solution, 8-12ml of OP-10 and 1.5-2.5g of nano carbon fiber into the dispersion liquid to obtain a ball abrasive;
B. ball milling is carried out on ball grinding materials, ball milling balls are taken out after ball milling is finished, and the ball milling materials are frozen and dried to obtain gel-like materials;
C. carbonizing the gel material at 850-950 ℃ in inert gas atmosphere to obtain the nano porous carbon additive.
As a preferred embodiment of the invention, the freezing step is specifically to freeze the ball-milling material at a temperature below-196 ℃ for 8-12min, and then freeze the ball-milling material at a temperature of-75 ℃ for 20-30h.
As a preferred embodiment of the present invention, the 65-75wt% phytic acid solution is a solution of 65-75wt% phytic acid and the balance being water.
As a preferred embodiment of the present invention, the molecular weight of chitosan is 2000.
As a preferred embodiment of the present invention, the length of the nano-sized carbon fiber is 5-8mm and the particle size is 40-60 μm.
As a preferred embodiment of the invention, the ultrasonic dispersion time is 20-40min, and the ultrasonic power is 100-150W.
As a preferred embodiment of the invention, the ball milling time is 3.5-4.5 hours, and the mass ratio of ball milling beads to ball milling materials is 4-6:1, the ball milling rotating speed is 450-550 rpm.
As a preferred embodiment of the present invention, the drying is specifically vacuum drying for 30 to 40 hours.
As a preferred embodiment of the invention, the carbonization step is specifically to continuously introduce protective gas at a rate of 18-22 mL/min, firstly raise the temperature from room temperature to 400+/-10 ℃ at a rate of 1.5-2.0 ℃/min, then raise the temperature to 850-950 ℃ at a rate of 2.2-2.5 ℃/min, and then maintain the temperature for 2.5-3.5 h.
Subject matter II
The application of the nano porous carbon additive for rubber engineering equipment, which is obtained by the preparation method provided by the technical subject one, in the rubber field.
As a preferred embodiment of the invention, the application is that in the step of preparing the rubber support, the nano porous carbon additive is ball-milled to obtain nano porous carbon additive powder, and the addition amount of the nano porous carbon additive is 2-20wt% of the rubber raw material.
As a preferred embodiment of the invention, the rubber support is made of natural rubber.
The preparation process of the rubber support comprises the following steps: placing natural rubber into an internal mixer, adding the nano porous carbon additive, plasticating for 15 minutes at 140 ℃, cutting and turning for three times on the internal mixer, and then injecting into a support mold for cooling to obtain the rubber support.
The beneficial effects of adopting above-mentioned technical scheme to produce lie in:
in the preparation method of the carbon material, the components are matched and cooperated, and can be fully contacted with rubber after being applied to the rubber, so that the rubber can be effectively reinforced.
In the invention, silicon carbide increases the friction of the material and reduces the wear rate; the carbon fiber improves the stretchability and the breaking elongation of the material, and OP-10, namely polyoxyethylene octyl phenol ether-10 accelerates the formation of sol-gel and solidifies the silicon carbide and the carbon fiber.
Drawings
FIG. 1 is a TEM image of a nanoporous carbon additive prepared according to example 3 of the invention;
FIG. 2 is an XPS diagram of the nano-porous carbon additive silicon prepared in example 3 of the present invention;
FIG. 3 is a graph showing the specific surface area of the nano-porous carbon additive prepared in example 3 of the present invention;
FIG. 4 is a graph showing pore size distribution of a nanoporous carbon additive prepared in example 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be clearly and completely described in connection with the following specific embodiments.
Each of the substances used in the following examples and comparative examples is commercially available.
Chitosan is purchased from Shanghai Ala Biochemical technology Co., ltd., product number C434553, and has a molecular weight of 2000;
OP-10, purchased from Shanghai Ala Biochemical technologies Co., ltd., product number O113278, hydroxyl number 87.+ -.10.
Example 1
The preparation method of the nano porous carbon additive for the rubber engineering equipment comprises the following steps:
A. adding 4g of silicon carbide into 270ml of deionized water, then performing ultrasonic dispersion for 20min, and obtaining dispersion liquid with ultrasonic power of 100W; adding 25g of chitosan, 15ml of 75wt% phytic acid solution, 12ml of OP-10 and 1.5g of nano-carbon fiber into the dispersion liquid to obtain a ball abrasive; the length of the nano-scale carbon fiber is 6mm, and the particle size is 50 microns;
B. ball milling the ball milling material in Germany fly high speed ball mill for 4.5h at the rotation speed of 450 r/min and the mass ratio of ball milling ball to ball milling material of 6:1, taking out ball-milling beads after ball milling, putting the ball-milling material into 2.0L liquid nitrogen to be frozen for 8min, then putting the ball-milling material into a freezer to be frozen for 30h at the temperature of 75 ℃ below zero, and then putting the ball-milling material into a room temperature vacuum dryer to be dried for 30h in vacuum to obtain a gel-like material;
C. and placing the gel material in a carbonization furnace, continuously introducing protective gas at the speed of 22mL/min, firstly heating to 400+/-10 ℃ from room temperature at the speed of 1.5 ℃/min, then heating to 850 ℃ at the speed of 2.5 ℃/min, and then maintaining for 3.5h to obtain the nano porous carbon additive.
The parameters of the prepared nano porous carbon additive are as follows: the specific surface area is 1091 m2/g, and the pore diameter is 4.2nm.
Example 2
The preparation method of the nano porous carbon additive for the rubber engineering equipment comprises the following steps:
A. adding 6g of silicon carbide into 230ml of deionized water, and then performing ultrasonic dispersion for 40min with ultrasonic power of 150W to obtain a dispersion liquid; 15g of chitosan, 25ml of 65wt% phytic acid solution, 8ml of OP-10 and 2.5g of nano-carbon fiber are added into the dispersion liquid to obtain a ball abrasive; the length of the nano-scale carbon fiber is 6mm, and the particle size is 50 microns;
B. ball milling the ball milling material in a German fly high-speed ball mill for 3.5h, wherein the ball milling rotating speed is 550 r/min, and the mass ratio of ball milling beads to ball milling material is 4:1, taking out ball-milling beads after ball milling, putting the ball-milling material into 2.0L liquid nitrogen to be frozen for 12min, then putting the ball-milling material into a freezer to be frozen for 20h at the temperature of 75 ℃ below zero, and then putting the ball-milling material into a room temperature vacuum dryer to be dried for 40h in vacuum to obtain a gel-like material;
C. and placing the gel material in a carbonization furnace, continuously introducing protective gas at the rate of 18mL/min, firstly heating to 400+/-10 ℃ from room temperature at the rate of 2.0 ℃/min, then heating to 950 ℃ at the rate of 2.2 ℃/min, and then maintaining for 2.5h to obtain the nano porous carbon additive.
The parameters of the prepared nano porous carbon additive are as follows: the specific surface area is 1179m2/g, and the pore diameter is 3.8nm.
Example 3
The preparation method of the nano porous carbon additive for the rubber engineering equipment comprises the following steps:
A. adding 5g of silicon carbide into 250ml of deionized water, and then performing ultrasonic dispersion for 30min with ultrasonic power of 120W to obtain a dispersion liquid; adding 20g of chitosan, 20ml of 70wt% phytic acid solution, 10ml of OP-10 and 2g of nano-carbon fiber into the dispersion liquid to obtain a ball abrasive; the length of the nano-scale carbon fiber is 6mm, and the particle size is 50 microns;
B. ball milling the ball milling material in a German fly high-speed ball mill for 4 hours, wherein the ball milling rotating speed is 500 revolutions per minute, and the mass ratio of ball milling beads to ball milling material is 5:1, taking out ball-milling beads after ball milling, putting the ball-milling material into 2.0L liquid nitrogen to be frozen for 10min, then putting the ball-milling material into a freezer to be frozen for 24h at the temperature of 75 ℃ below zero, and then putting the ball-milling material into a room temperature vacuum dryer to be dried for 36h in vacuum to obtain a gel-like material;
C. and placing the gel material in a carbonization furnace, continuously introducing protective gas at the speed of 20mL/min, firstly heating to 400+/-10 ℃ from room temperature at the speed of 1.5 ℃/min, then heating to 900 ℃ at the speed of 2.4 ℃/min, and then maintaining for 3 hours to obtain the nano porous carbon additive.
The parameters of the prepared nano porous carbon additive are as follows: specific surface area 1560 m2/g, pore diameter 3.2nm.
As shown in fig. 1, it can be seen that the carbon fibers are obviously dispersed in the nano porous carbon additive structure, as shown in fig. 2, a silicon signal peak is seen, and that the nano porous carbon additive of the invention is successfully doped with silicon element, that is, silicon carbide is doped into the nano porous carbon additive structure, as shown in fig. 3, the adsorption-desorption curve can be seen to have higher adsorption capacity, as shown in fig. 4, the pore diameter distribution diagram can be seen to be mainly microporous, and the pore diameter is smaller than 5nm.
Example 4
The preparation method of the nano porous carbon additive for the rubber engineering equipment comprises the following steps:
A. adding 5g of silicon carbide into 250ml of deionized water, and then performing ultrasonic dispersion for 40min with ultrasonic power of 100W to obtain a dispersion liquid; 21g of chitosan, 22ml of 75wt% phytic acid solution, 9ml of OP-10 and 2g of nano-carbon fiber are added into the dispersion liquid to obtain a ball abrasive; the length of the nano-scale carbon fiber is 6mm, and the particle size is 50 microns;
B. ball milling the ball milling material in a German fly high-speed ball mill for 4 hours, wherein the ball milling rotating speed is 500 revolutions per minute, and the mass ratio of ball milling beads to ball milling material is 5:1, taking out ball-milling beads after ball milling, putting the ball-milling material into 2.0L liquid nitrogen to be frozen for 10min, then putting the ball-milling material into a freezer to be frozen for 24h at the temperature of 75 ℃ below zero, and then putting the ball-milling material into a room temperature vacuum dryer to be dried for 36h in vacuum to obtain a gel-like material;
C. and placing the gel material in a carbonization furnace, continuously introducing protective gas at the speed of 20mL/min, firstly heating to 400+/-10 ℃ from room temperature at the speed of 1.5 ℃/min, then heating to 900 ℃ at the speed of 2.4 ℃/min, and then maintaining for 3 hours to obtain the nano porous carbon additive.
The parameters of the prepared nano porous carbon additive are as follows: specific surface area 984 m2/g, pore size 2.8nm.
Comparative example 1
The preparation method of the nano porous carbon additive for the rubber engineering equipment comprises the following steps:
A. adding 5g of silicon carbide into 250ml of deionized water, and then performing ultrasonic dispersion for 30min with ultrasonic power of 120W to obtain a dispersion liquid; adding 20g of chitosan, 20ml of 70wt% phytic acid solution and 10ml of OP-10 into the dispersion liquid to obtain a ball abrasive;
B. ball milling the ball milling material in a German fly high-speed ball mill for 4 hours, wherein the ball milling rotating speed is 500 revolutions per minute, and the mass ratio of ball milling beads to ball milling material is 5:1, taking out ball-milling beads after ball milling, putting the ball-milling material into 2.0L liquid nitrogen to be frozen for 10min, then putting the ball-milling material into a freezer to be frozen for 24h at the temperature of 75 ℃ below zero, and then putting the ball-milling material into a room temperature vacuum dryer to be dried for 36h in vacuum to obtain a gel-like material;
C. and placing the gel material in a carbonization furnace, continuously introducing protective gas at the speed of 20mL/min, firstly heating to 400+/-10 ℃ from room temperature at the speed of 1.5 ℃/min, then heating to 900 ℃ at the speed of 2.4 ℃/min, and then maintaining for 3 hours to obtain the nano porous carbon additive.
The parameters of the prepared nano porous carbon additive are as follows: specific surface area 1503 m2/g, pore size 8.6nm.
Comparative example 2
The preparation method of the nano porous carbon additive for the rubber engineering equipment comprises the following steps:
A. adding 20g of chitosan, 20ml of 70wt% phytic acid solution, 10ml of OP-10 and 2g of nano-carbon fiber into 250ml of deionized water to obtain a ball abrasive; the length of the nano-scale carbon fiber is 6mm, and the particle size is 50 microns;
B. ball milling the ball milling material in a German fly high-speed ball mill for 4 hours, wherein the ball milling rotating speed is 500 revolutions per minute, and the mass ratio of ball milling beads to ball milling material is 5:1, taking out ball-milling beads after ball milling, putting the ball-milling material into 2.0L liquid nitrogen to be frozen for 10min, then putting the ball-milling material into a freezer to be frozen for 24h at the temperature of 75 ℃ below zero, and then putting the ball-milling material into a room temperature vacuum dryer to be dried for 36h in vacuum to obtain a gel-like material;
C. and placing the gel material in a carbonization furnace, continuously introducing protective gas at the speed of 20mL/min, firstly heating to 400+/-10 ℃ from room temperature at the speed of 1.5 ℃/min, then heating to 900 ℃ at the speed of 2.4 ℃/min, and then maintaining for 3 hours to obtain the nano porous carbon additive.
The parameters of the prepared nano porous carbon additive are as follows: specific surface area 1498 m2/g, pore size 7.6nm.
Comparative example 3
The preparation method of the nano porous carbon additive for the rubber engineering equipment comprises the following steps:
A. adding 5g of silicon carbide into 250ml of deionized water, and then performing ultrasonic dispersion for 30min with ultrasonic power of 120W to obtain a dispersion liquid; adding 20g of chitosan, 20ml of 70wt% phytic acid solution and 2g of nano carbon fiber into the dispersion liquid to obtain a ball abrasive; the length of the nano-scale carbon fiber is 6mm, and the particle size is 50 microns;
B. ball milling the ball milling material in a German fly high-speed ball mill for 4 hours, wherein the ball milling rotating speed is 500 revolutions per minute, and the mass ratio of ball milling beads to ball milling material is 5:1, taking out ball-milling beads after ball milling, putting the ball-milling material into 2.0L liquid nitrogen to be frozen for 10min, then putting the ball-milling material into a freezer to be frozen for 24h at the temperature of 75 ℃ below zero, and then putting the ball-milling material into a room temperature vacuum dryer to be dried for 36h in vacuum to obtain a gel-like material;
C. and placing the gel material in a carbonization furnace, continuously introducing protective gas at the speed of 20mL/min, firstly heating to 400+/-10 ℃ from room temperature at the speed of 1.5 ℃/min, then heating to 900 ℃ at the speed of 2.4 ℃/min, and then maintaining for 3 hours to obtain the nano porous carbon additive.
The parameters of the prepared nano porous carbon additive are as follows: specific surface area 792 m2/g, pore diameter 10.6nm.
Comparative example 4
The preparation method of the nano porous carbon additive for the rubber engineering equipment comprises the following steps:
A. adding 5g of silicon carbide into 250ml of deionized water, and then performing ultrasonic dispersion for 30min with ultrasonic power of 120W to obtain a dispersion liquid; adding 20g of chitosan, 10ml of OP-10 and 2g of nano carbon fiber into the dispersion liquid to obtain a ball abrasive; the length of the nano-scale carbon fiber is 6mm, and the particle size is 50 microns;
B. ball milling the ball milling material in a German fly high-speed ball mill for 4 hours, wherein the ball milling rotating speed is 500 revolutions per minute, and the mass ratio of ball milling beads to ball milling material is 5:1, taking out ball-milling beads after ball milling, putting the ball-milling material into 2.0L liquid nitrogen to be frozen for 10min, then putting the ball-milling material into a freezer to be frozen for 24h at the temperature of 75 ℃ below zero, and then putting the ball-milling material into a room temperature vacuum dryer to be dried for 36h in vacuum to obtain a gel-like material;
C. and placing the gel material in a carbonization furnace, continuously introducing protective gas at the speed of 20mL/min, firstly heating to 400+/-10 ℃ from room temperature at the speed of 1.5 ℃/min, then heating to 900 ℃ at the speed of 2.4 ℃/min, and then maintaining for 3 hours to obtain the nano porous carbon additive.
The parameters of the prepared nano porous carbon additive are as follows: the specific surface area is 836 m2/g, and the pore diameter is 12.3nm.
Comparative example 5
The preparation method of the nano porous carbon additive for the rubber engineering equipment comprises the following steps:
A. adding 5g of silicon carbide into 250ml of deionized water, and then performing ultrasonic dispersion for 30min with ultrasonic power of 120W to obtain a dispersion liquid; adding 20g of chitosan and 2g of nano-carbon fiber into the dispersion liquid to obtain a ball abrasive; the length of the nano-scale carbon fiber is 6mm, and the particle size is 50 microns;
B. ball milling the ball milling material in a German fly high-speed ball mill for 4 hours, wherein the ball milling rotating speed is 500 revolutions per minute, and the mass ratio of ball milling beads to ball milling material is 5:1, taking out ball-milling beads after ball milling, putting the ball-milling material into 2.0L liquid nitrogen to be frozen for 10min, then putting the ball-milling material into a freezer to be frozen for 24h at the temperature of 75 ℃ below zero, and then putting the ball-milling material into a room temperature vacuum dryer to be dried for 36h in vacuum to obtain a gel-like material;
C. and placing the gel material in a carbonization furnace, continuously introducing protective gas at the speed of 20mL/min, firstly heating to 400+/-10 ℃ from room temperature at the speed of 1.5 ℃/min, then heating to 900 ℃ at the speed of 2.4 ℃/min, and then maintaining for 3 hours to obtain the nano porous carbon additive.
The parameters of the prepared nano porous carbon additive are as follows: the specific surface area was 709 m2/g, and the pore diameter was 13.8nm.
Comparative example 6
The preparation method of the nano porous carbon additive for the rubber engineering equipment comprises the following steps:
A. adding 5g of silicon carbide into 250ml of deionized water, and then performing ultrasonic dispersion for 30min with ultrasonic power of 120W to obtain a dispersion liquid; adding 20g of chitosan, 20ml of 70wt% phytic acid solution, 10ml of hydroxyethyl cellulose (Aba Ding Shiji, 1000-1500 mpa.s) and 2g of nano-carbon fiber into the dispersion liquid to obtain a ball abrasive; the length of the nano-scale carbon fiber is 6mm, and the particle size is 50 microns;
B. ball milling the ball milling material in a German fly high-speed ball mill for 4 hours, wherein the ball milling rotating speed is 500 revolutions per minute, and the mass ratio of ball milling beads to ball milling material is 5:1, taking out ball-milling beads after ball milling, putting the ball-milling material into 2.0L liquid nitrogen to be frozen for 10min, then putting the ball-milling material into a freezer to be frozen for 24h at the temperature of 75 ℃ below zero, and then putting the ball-milling material into a room temperature vacuum dryer to be dried for 36h in vacuum to obtain a gel-like material;
C. and placing the gel material in a carbonization furnace, continuously introducing protective gas at the speed of 20mL/min, firstly heating to 400+/-10 ℃ from room temperature at the speed of 1.5 ℃/min, then heating to 900 ℃ at the speed of 2.4 ℃/min, and then maintaining for 3 hours to obtain the nano porous carbon additive.
The parameters of the prepared nano porous carbon additive are as follows: specific surface area 721 m2/g, pore size 15.6nm.
Application examples
The nanoporous carbon additives prepared in examples 1 to 4 and comparative examples 1 to 6 were prepared into rubber supports by the following method:
the natural rubber was placed in an internal mixer, then a certain amount of a nanoporous carbon additive was added (the addition amount of the nanoporous carbon additive was 2 to 20% by weight of the rubber raw material, and examples 1 to 4 and comparative examples 1 to 6 were respectively added with 2% by weight, 5% by weight, 10% by weight, 20% by weight, 10% by weight, and 10% by weight), plasticated for 15 minutes at 140 ℃, cut and turned three times on the internal mixer, and then injected into a support mold to be cooled to obtain a rubber support. The natural rubber was purchased from Shanghai Reed Polymer materials Inc., full latex (cat number: SCRWF).
The friction performance (wear rate) of the obtained rubber support is detected according to the JT/T901-2014 annex B sliding plate line wear test method standard:
the indoor temperature is 21 ℃, and the indoor humidity is controlled to be 40-50% by adopting a compressed air freeze dryer. The temperature of the rubber support and the stainless steel plate is controlled to be 21 ℃ by introducing circulating flowing alcohol into the stainless steel sliding layer, the test is carried out on an abrasion tester, a test piece is installed by adopting a method of embedding four dew three, the friction sliding speed is 15mm/s, the pressure stress is uniformly 45MPa, the sine wave loading is adopted, and the single-side sliding distance is 10mm. The results are shown in Table 1 below.
The tensile strength measurement method comprises the following steps:
1. preparation of experiments
The rubber was subjected to uniaxial stretching experiments, and test pieces of the rubber were prepared according to national standards. The cutter used in the test meets the requirements of GB/T2941, and a punching device is used for cutting the manufactured rubber test piece.
(1) Thickness gauge
The thickness of the sample may be measured by a thickness gauge in accordance with the specification of GB/T2941 method A. When the thickness of the sample wafer is measured by a thickness gauge, 3 measurement values should be taken to measure the thickness of the sample wafer, and the thickness is measured at the middle and the two ends respectively. Typically, an average of three thicknesses may be selected for calculating the cross-sectional area of the specimen. The values of the three thicknesses determined should be close to the average, as desired. The distance between the edges of the narrow portion of the cutter was taken as the thickness of the sample, and the measurement was performed in accordance with the specification of GB/T2941, and the accuracy was required to be 0.05mm.
(2) Test fixture
Because the testing machine is provided with the upper clamp and the lower clamp, the test sample is required to be clamped symmetrically when the test is carried out, and thus the test sample can be subjected to uniform tensile force. If necessary, an elongation measuring device is provided. The testing machine is started, the change of the test length and force is continuously monitored in the whole test process, and the precision is within the range of about 2%. Movement speed of gripper: 1. the type and type 2 samples should be 500 mm/min.+ -. 50mm/min. The clamp of the tensile machine is made of metal materials, and the sample is clamped manually. The contact between the clamp and the rubber has a plurality of small teeth to increase the friction system between the clamp and the rubber, so that the test sample can work stably during the stretching process. When the sample is cut, the cutting is performed by a punching device. And selecting type 1 and type 2 cutters to cut type 1 and type 2 samples respectively. The film is placed on the cardboard, then the punch is placed on top of the film, and the button is pressed to die cut.
2. Experimental procedure
1. Experimental procedure
According to the requirement, the sample wafer is clamped on an upper clamping piece and a lower clamping piece of the tension machine, and according to the standard experiment size, the sample is clamped and fixed within the effective test range, so that the stable state is achieved. After the sample is clamped stably, parameters are set, test work is started, and test data are recorded. For the type 1 and type 2 samples, the moving speed was 500 mm/min.+ -. 50mm according to the prescribed standard. During the experiment, if the sample breaks in the area other than the narrow portion, the set of experimental data needs to be discarded and another sample is taken for re-measurement.
2. Test temperature
The test was carried out at the temperature specified in GB/T2941.
3. Experimental calculation
(1) Tensile strength TS, the tensile strength refers to the maximum tensile stress of a sample at break, and the mathematical expression is:
wherein TS is expressed in units of MPa,
f is the force applied, in N,
w is the width of the narrowest part in the middle of the cutter,
t is the average value of the measured thickness of the sample, and the unit is mm.
(2) Elongation at break Eb, which is the elongation of a sample at break, is expressed in terms of
Wherein Eb units are as follows;
l1 is the distance when the sample piece breaks, the unit is mm,
l0 is the initial gauge length of the dailies in mm.
3. Testing
When stretching rubber, dumbbell-shaped test pieces are adopted because uniaxial stretching experiments have national standards. The rubber sample at break is shown as broken from the gauge length and is not effective if the break does not occur in the test area.
The effective lengths of the rubber dumbbell type test samples specified by national standards are as follows:
type 2 samples were selected for testing in this experiment and the results are shown in table 1 below.
Claims (10)
1. The preparation method of the nano porous carbon additive for the rubber engineering equipment is characterized by comprising the following steps of:
A. adding 4-6g of silicon carbide into 230-270ml of deionized water, and then performing ultrasonic dispersion to obtain a dispersion liquid; adding 15-25g of chitosan, 15-25ml of 65-75wt% phytic acid solution, 8-12ml of OP-10 and 1.5-2.5g of nano carbon fiber into the dispersion liquid to obtain a ball abrasive;
B. ball milling is carried out on ball grinding materials, ball milling balls are taken out after ball milling is finished, and the ball milling materials are frozen and dried to obtain gel-like materials;
C. carbonizing the gel material at 850-950 ℃ in inert gas atmosphere to obtain the nano porous carbon additive.
2. The method for preparing the nano-porous carbon additive for rubber engineering equipment according to claim 1, wherein the freezing step is specifically to freeze the ball mill material below-196 ℃ for 8-12min, and then to freeze the ball mill material at-75 ℃ for 20-30h.
3. The method for preparing a nano-porous carbon additive for rubber engineering equipment according to claim 1, wherein the molecular weight of the chitosan is 2000.
4. The method for preparing the nano-porous carbon additive for rubber engineering equipment according to claim 1, wherein the length of the nano-scale carbon fiber is 5-8mm, and the particle size is 40-60 microns.
5. The method for preparing the nano-porous carbon additive for rubber engineering equipment according to claim 1, wherein the ultrasonic dispersion time is 20-40min and the ultrasonic power is 100-150W.
6. The method for preparing the nano porous carbon additive for rubber engineering equipment according to claim 1, wherein the ball milling time is 3.5-4.5h, and the mass ratio of ball milling beads to ball milling materials is 4-6:1, the ball milling rotating speed is 450-550 rpm.
7. The method for preparing the nano-porous carbon additive for rubber engineering equipment according to claim 1, wherein the drying is specifically vacuum drying for 30-40h.
8. The preparation method of the nano porous carbon additive for rubber engineering equipment according to claim 1, wherein the carbonization step is characterized in that shielding gas is continuously introduced at a rate of 18-22 mL/min, the temperature is firstly increased to 400+/-10 ℃ from room temperature at a rate of 1.5-2.0 ℃/min, and then the temperature is increased to 850-950 ℃ at a rate of 2.2-2.5 ℃/min, and then the temperature is kept for 2.5-3.5 h.
9. Use of the nanoporous carbon additive for rubber engineering equipment obtained by the preparation process according to any one of claims 1 to 8 in the rubber field.
10. The use according to claim 9, wherein in the step of preparing the rubber support, the nano-porous carbon additive is added in an amount of 2-20wt% of the rubber raw material.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150094399A1 (en) * | 2013-09-30 | 2015-04-02 | Hitachi Metals, Ltd. | Elastic composite material and mold product using the same |
| CN107936916A (en) * | 2017-11-09 | 2018-04-20 | 马鞍山市心洲葡萄专业合作社 | A kind of preparation method of modified carbon fiber friction particles |
| CN108231425A (en) * | 2017-12-28 | 2018-06-29 | 盐城工学院 | It is a kind of for nitrogen-phosphor codoping porous carbon of electrode material for super capacitor and preparation method thereof |
| CN109516457A (en) * | 2018-12-05 | 2019-03-26 | 华南师范大学 | A kind of chitosan-based porous carbon ball and preparation method thereof |
| CN110003536A (en) * | 2019-02-20 | 2019-07-12 | 谭美英 | A kind of preparation method of heat-dissipation type wear-resistant rubber material |
| CN114146679A (en) * | 2021-12-15 | 2022-03-08 | 中南林业科技大学 | Millimeter-grade nitrogen-doped porous carbon sphere and preparation and application thereof |
| CN115124024A (en) * | 2022-08-04 | 2022-09-30 | 安徽固瑞特新材料科技有限公司 | Porous carbon material, composite rubber filler, preparation method of composite rubber filler and rubber material |
| CN116376127A (en) * | 2023-03-16 | 2023-07-04 | 杭州珠玛实业有限公司 | Anti-cracking wear-resistant material for magnetic toy and preparation method thereof |
-
2023
- 2023-10-19 CN CN202311352774.6A patent/CN117088360B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150094399A1 (en) * | 2013-09-30 | 2015-04-02 | Hitachi Metals, Ltd. | Elastic composite material and mold product using the same |
| CN107936916A (en) * | 2017-11-09 | 2018-04-20 | 马鞍山市心洲葡萄专业合作社 | A kind of preparation method of modified carbon fiber friction particles |
| CN108231425A (en) * | 2017-12-28 | 2018-06-29 | 盐城工学院 | It is a kind of for nitrogen-phosphor codoping porous carbon of electrode material for super capacitor and preparation method thereof |
| CN109516457A (en) * | 2018-12-05 | 2019-03-26 | 华南师范大学 | A kind of chitosan-based porous carbon ball and preparation method thereof |
| CN110003536A (en) * | 2019-02-20 | 2019-07-12 | 谭美英 | A kind of preparation method of heat-dissipation type wear-resistant rubber material |
| CN114146679A (en) * | 2021-12-15 | 2022-03-08 | 中南林业科技大学 | Millimeter-grade nitrogen-doped porous carbon sphere and preparation and application thereof |
| CN115124024A (en) * | 2022-08-04 | 2022-09-30 | 安徽固瑞特新材料科技有限公司 | Porous carbon material, composite rubber filler, preparation method of composite rubber filler and rubber material |
| CN116376127A (en) * | 2023-03-16 | 2023-07-04 | 杭州珠玛实业有限公司 | Anti-cracking wear-resistant material for magnetic toy and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 詹益兴主编: "现代化工小商品制法大全 第2集", 湖南大学出版社, pages: 167 - 47 * |
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