CN106336546B - A kind of tread rubber of automobile tires of graphene-containing - Google Patents
A kind of tread rubber of automobile tires of graphene-containing Download PDFInfo
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- CN106336546B CN106336546B CN201510414599.8A CN201510414599A CN106336546B CN 106336546 B CN106336546 B CN 106336546B CN 201510414599 A CN201510414599 A CN 201510414599A CN 106336546 B CN106336546 B CN 106336546B
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- graphene
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- automobile tires
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Abstract
A kind of tread rubber of automobile tires of graphene-containing is uniformly mixed with graphene and/or graphene composite material that mass fraction is 5 ~ 30% in the sizing material of the tire tread glue；The raw material for preparing of the graphene and graphene composite material is the waste material after diamond production.Graphene and/or graphene composite material are dispersed in the sizing material of automobile tire by the present invention, graphene is distributed across just as net in tyre stock, better tread rubber is obtained, the wearability, resistance to pressure and thermal diffusivity of tire can be greatly improved, to improve the safety of traveling；Pollution-free in addition, can save material, cost reduces by 50% 80% compared to graphite raw material.
Description
Technical field
The present invention relates to tire manufacturing techniques field, especially a kind of tread rubber of automobile tires of graphene-containing.
Background technology
Automobile is the most important thing in modern society's vehicles, as the high speed of auto industry and transportation is sent out
Exhibition, the fast development of highway construction especially highway, demand of the people to high-performing car tire are more and more urgent.However
Existing overwhelming majority tire is all easy to rupture, and has the wretched insufficiency in terms of wearability and resistance to pressure, encounters mal-condition
It also occurs that explosion, therefore, needs to improve these disadvantages of tire.
Graphene is by graphite flake stripping at obtaining after single layer only there are one the flat film of carbon atom thickness, is the world
Upper known most thin, most hard nano material, taller 200 times best of steel of its intensity specific mass, this is like needing
It allows an elephant station on a pencil, the graphene thin layer of a fresh-keeping film thickness could be pierced through.The structure ten of graphene
Divide and stablize, the connection between each carbon atom is very flexible, and when an external force is applied, carbon atom face is with regard to flexural deformation, to keep carbon former
Son need not rearrange also can holding structure stabilization.From the perspective of surface chemistry, the property of graphene is similar to graphite, can
To adsorb and be desorbed various atoms and molecule, its specific surface area is up to 2600 m2/ g has the premise item of fabulous absorption
Part.
The certain technological means of diamond（Such as static ultrahigh pressure and high-temperature technology）Pass through the carbon raw materials such as graphite
With certain metals（Alloy）Reaction generates diamond.The main application of diamond is：It, can using the hardness of diamond
Tools, such as cutter, drill bit, saw blade；Using the aesthetic feeling of diamond, diamond, jewel and ornament etc. can be made.By
Diamond after processing will produce a pile waste material, and usual people can throw away diamond waste material so that in waste material
Graphite material not put into other application field, not only pollute environment, but also waste material, improve cost.
Invention content
Technical problem to be solved by the present invention lies in a kind of graphene-containings with high-wearing feature and resistance to pressure of offer
Tread rubber of automobile tires.
The technical scheme is that：A kind of tread rubber of automobile tires of graphene-containing, the sizing material of the tire tread glue
Include the graphene and/or graphene composite material that mass fraction is 5 ~ 30%；The graphene and graphene composite material
It is the waste material after diamond production to prepare raw material.
Further, the waste material after diamond production includes unstripped useless of graphite waste material, the graphite removed
Material and diamond waste material；The weight for the waste material that the graphite has been removed is not less than the waste material weight after diamond production
10%；The weight percent of the diamond waste material is 0.05% ~ 0.5%.
Further, the graphene is single-layer sheet or multilayer tablet, and the thickness of single-layer sheet is 0.35nm, length is 0.1 ~
50um。
Further, in the form of sheets, thickness is 0.35 ~ 300nm to the graphene composite material, and length is 0.1 ~ 50um.
Further, the unstripped waste material of the graphite has been removed waste material and graphite is in bulk.
Further, the sizing material of the tire tread glue includes that mass fraction is multiple for 6 ~ 18% graphene and/or graphene
Condensation material.
Further, the sizing material of the tire tread glue includes the graphene and/or graphene that mass fraction is 19 ~ 29%
Composite material.
Further, the preparation method of the graphene includes the following steps：
（1）The waste material directly or is after pretreatment scattered in solvent, is then added in steam explosion high-pressure bottle, in temperature
Degree is 0.5 ~ 10h of heat preservation under conditions of room temperature ~ 400 DEG C, and then the pressure in steam explosion high-pressure bottle is pressurizeed by pressurized equipment
To 20MPa ~ 300MPa, moment release；
（2）The product obtained after release is centrifuged or is vaporized and is dried to obtain graphene.
Further, the pretreatment mode of the waste material is ball milling waste material, handles waste material using homogenizer, is ultrasonically treated waste material
In a kind of mode or several mode is used in combination.
Further, the preparation method of the graphene composite material includes the following steps：
Step（1）~（2）As described in the preparation method of graphene；
（3）The graphene of constant weight is put into sonic oscillation in deionized water and disperses 30min, then filters and moves to saturation
SnCl2Then sonic oscillation 40-60min in solution is filtered and is moved to PdCl2Sonic oscillation 40-60min in solution is filtered and is spent
Ion water washing to neutrality is dried in vacuo；
（4）A certain amount of nickeliferous readily soluble compound is weighed, is mixed with ammonium chloride, sodium citrate, addition deionized water is prepared molten
Liquid is used in combination ammonium hydroxide to be adjusted to PH to 10；
（5）To step（4）Mixed solution in add step（3）Then the graphene of preparation, 30 min of ultrasonic disperse add
Enter 5% sodium hypophosphite aqueous solution, adjust PH to 10,60 min are stirred at 40 DEG C, after the reaction was complete, washs, it is dry, it obtains
Graphene composite material.
The present invention has following features compared with prior art：
（1）High abrasion, high voltage, high intensity.Graphene and/or graphene composite material are dispersed in automobile tire
Sizing material in, graphene is distributed across just as net in tyre stock, obtains better tread rubber, and tire can be greatly improved
Wearability, resistance to pressure and thermal diffusivity, to improve the safety of traveling.
（2）Waste material recoverable, it is at low cost.Waste material after being produced using diamond prepares graphene,
It can save material, pollution-free, cost reduces 50%-80% compared to graphite raw material.
（3）Stripping rate is high.Can include the waste material that part graphite has been removed in waste material after being produced due to diamond,
It is easier to make graphene in this way, under conditions of further high pressure is removed, 10%- is improved relative to graphite raw material stripping rate
40%.
（4）Graphene composite material wearability is good.Can include diamond in waste material after being produced due to diamond,
So that the graphene composite material hardness prepared is big, wearability is good, under identical working condition, relative to graphite raw material,
The wear extent of its tire tread glue made reduces 10-30%.
（5）Tensile strength is big.The graphene prepared in the form of sheets, can reinforce the tensile strength between sizing material.
Specific implementation mode
Technical scheme of the present invention is described in further detail below in conjunction with specific implementation mode.
A kind of tread rubber of automobile tires of graphene-containing, it is 5 ~ 30% that the sizing material of tire tread glue, which includes mass fraction,
Graphene and/or graphene composite material；The raw material for preparing of graphene and graphene composite material produces for diamond
Waste material afterwards, the waste material include the unstripped waste material and diamond waste material of graphite waste material, the graphite removed；What graphite had been removed
10% of the weight of waste material not less than the waste material weight after diamond production；The weight percent of diamond waste material is
0.05% ~ 0.5%.
The method for preparing graphene and its composite material using diamond waste material, includes the following steps：
（1）Above-mentioned waste material 100g directly or is after pretreatment scattered in solvent, is then added in steam explosion high-pressure bottle,
0.5 ~ 10h is kept the temperature under conditions of temperature is room temperature ~ 400 DEG C, then by pressurized equipment by the pressure in steam explosion high-pressure bottle
After being forced into 20MPa ~ 300MPa, moment release；
（2）The product obtained after release is centrifuged or is vaporized and is dried to obtain graphene 80g ~ 98g.
（3）1g graphenes are put into sonic oscillation in deionized water and disperse 30min, then filters and moves to 100ml saturations SnCl2
Then sonic oscillation 40-60min in solution filters the PdCl for moving to a concentration of 1g/L of 100ml2Sonic oscillation 40- in solution
60min is filtered and is washed with deionized to neutrality vacuum drying；
（4）1.15g nickel sulfates, 1.59g ammonium chlorides, the mixing of 0.54g sodium citrates are weighed, addition deionized water prepares 70ml
Solution is used in combination ammonium hydroxide to be adjusted to PH to 10；
（5）To step（4）Mixed solution in add 0.1g graphenes, 30 min of ultrasonic disperse is then slowly added into
The sodium hypophosphite aqueous solution of 30ml5% adjusts PH to 10,60 min is stirred at 40 DEG C, after the reaction was complete, washs, dry, obtains
To graphene composite material.
For the waste material pretreatment mode after diamond production, identical, high pressure removes parameter under the same conditions to table 1,
The unstripped waste material of waste material that graphite has been removed, graphite with when diamond waste material proportion difference to graphene obtained and graphene
The influence of composite material wherein waste material pretreatment modes and high pressure stripping parameter take optimum way to be prepared, i.e.,：In ultrasonic machine
Middle addition 400ml ethyl alcohol adds the waste material after diamond production, room temperature, 1 h of ultrasound, then the ball in high energy ball mill
1.5 h are ground, are 1.5 h of homogeneous under 12000 r/min with homogeneous speed then in high-shear homogenizer；It will be pretreated useless
Material is dispersed in water and is placed in steam explosion high-pressure bottle, and 8h is kept the temperature under conditions of temperature is 400 DEG C, by pressurized equipment by vapour
After pressure in quick-fried high-pressure bottle is forced into 300MPa, moment release.
The content proportion of waste material after the different diamond productions of table 1 is to graphene obtained and its composite material
It influences
As can be seen from Table 1, as the content of diamond waste material increases, the hardness of graphene composite material also with
Increase；The content for the waste material removed with graphite increases, and the lamellar spacing of gained graphene is thinner, it is easier to
Single-layer graphene film is obtained, the thickness of obtained graphene composite material is also thinner.
On the basis of 1 illustrated embodiment 1 ~ 8 of table, into the sizing material of tire tread glue, evenly dispersed mass fraction is
10% by the graphene composite material obtained by embodiment 1 ~ 8, come analyze the elongation at break to tire tread glue, hardness and
The influence of tensile strength, is shown in Table 2.
Influence of the content proportion of waste material after the different diamond productions of table 2 to tire tread glue characteristic
As can be seen from Table 2, as the content of diamond waste material increases, the tire filled with graphene composite material
Elongation rate of tensile failure, tensile strength and the shore hardness of face glue all increased.
The content proportion of waste material after diamond production under the same conditions, by prepared graphene and/or
Graphene composite material is dispersed in the sizing material of tire tread glue, and difference composition and the shared weight percent of composition are shown in Table 3
It is shown.Such as：The preparation method of embodiment 9 is：The graphene uniform that mass fraction is 5% is scattered in the glue of tire tread glue
In material；Or the graphene composite material that mass fraction is 5% is scattered in the sizing material of tire tread glue；Or it is by matter
The graphene composite material mixing that the graphene and mass fraction that amount score is 5% are 5% is scattered in the sizing material of tire tread glue,
To obtain three kinds of different tread rubber of automobile tires.
The different compositions of table 3 and the shared loading percentage of composition
The influence of the elongation at break to tire tread glue, hardness and tensile strength is analyzed according to the different compositions of table 3,
It is shown in Table 4.
The different influences for organizing pairs of tire tread glue characteristic of table 4
Three numerical value composition different from each embodiment in table 3 of each characteristic in each embodiment of table 4
It is corresponding.As can be seen from Table 4, as the loading of graphene and graphene composite material increases, tire tread glue is broken
Elongation, tensile strength and shore hardness all increased.Graphene composite material performance is better than graphene, and graphene and stone
Black alkene composite material combination best performance.
It these are only the preferred embodiment of the present invention, be not intended to restrict the invention, it is clear that those skilled in the art can
To carry out various changes, modification without departing from the spirit and scope of the present invention to the present invention.If these modifications to the present invention
Within the scope of the claims of the present invention and its equivalent technology with modification, it all belongs to the scope of protection of the present invention.
Claims (9)
1. a kind of tread rubber of automobile tires of graphene-containing, it is characterised in that：The sizing material of the tire tread glue includes quality
The graphene and/or graphene composite material that score is 5 ~ 30%；The raw material for preparing of the graphene and graphene composite material is
Waste material after diamond production.
2. the tread rubber of automobile tires of graphene-containing according to claim 1, it is characterised in that：The diamond production
Waste material afterwards includes the unstripped waste material and diamond waste material of graphite waste material, the graphite removed；The graphite has been removed useless
10% of the weight of material not less than the waste material weight after diamond production；The weight percent of the diamond waste material is
0.05% ~ 0.5%.
3. the tread rubber of automobile tires of graphene-containing according to claim 1 or claim 2, it is characterised in that：The graphene is single
The thickness of synusia or multilayer tablet, single-layer sheet is 0.35nm, and length is 0.1 ~ 50 μm.
4. the tread rubber of automobile tires of graphene-containing according to claim 1 or claim 2, it is characterised in that：The graphene is compound
In the form of sheets, thickness is 0.35 ~ 300nm to material, and length is 0.1 ~ 50um.
5. the tread rubber of automobile tires of graphene-containing according to claim 2, it is characterised in that：The graphite has been removed useless
Material and the unstripped waste material of graphite are in bulk.
6. the tread rubber of automobile tires of graphene-containing according to claim 1 or claim 2, it is characterised in that：The tire tread glue
Sizing material include mass fraction be 6 ~ 18% graphene and/or graphene composite material.
7. the tread rubber of automobile tires of graphene-containing according to claim 1 or claim 2, it is characterised in that：The tire tread glue
Sizing material include mass fraction be 19 ~ 29% graphene and/or graphene composite material.
8. the tread rubber of automobile tires of graphene-containing according to claim 2, it is characterised in that：The preparation side of the graphene
Method includes the following steps：
（1）The waste material directly or is after pretreatment scattered in solvent, is then added in steam explosion high-pressure bottle, is in temperature
0.5 ~ 10h is kept the temperature under conditions of room temperature ~ 400 DEG C, is then forced into the pressure in steam explosion high-pressure bottle by pressurized equipment
After 20MPa ~ 300MPa, moment release；
（2）The product obtained after release is centrifuged or is vaporized and is dried to obtain graphene.
9. the tread rubber of automobile tires of graphene-containing according to claim 8, it is characterised in that：The pretreatment side of the waste material
Formula is ball milling waste material, waste material is handled using homogenizer, a kind of mode being ultrasonically treated in waste material or several mode is used in combination.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510414599.8A CN106336546B (en) | 2015-07-15 | 2015-07-15 | A kind of tread rubber of automobile tires of graphene-containing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510414599.8A CN106336546B (en) | 2015-07-15 | 2015-07-15 | A kind of tread rubber of automobile tires of graphene-containing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106336546A CN106336546A (en) | 2017-01-18 |
| CN106336546B true CN106336546B (en) | 2018-09-18 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1119985A (en) * | 1995-06-08 | 1996-04-10 | 李建国 | Manufacture technology of diamond rubber tyre |
| CN202098233U (en) * | 2011-04-26 | 2012-01-04 | 张德志 | Outer tire of graphene tire |
| CN103374150A (en) * | 2012-04-24 | 2013-10-30 | 住友橡胶工业株式会社 | Rubber composition for tread and pneumatic tire using the same for tread |
| CN104672572A (en) * | 2013-11-28 | 2015-06-03 | 大连轮胎厂有限公司 | Composite material composition for tires |
-
2015
- 2015-07-15 CN CN201510414599.8A patent/CN106336546B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1119985A (en) * | 1995-06-08 | 1996-04-10 | 李建国 | Manufacture technology of diamond rubber tyre |
| CN202098233U (en) * | 2011-04-26 | 2012-01-04 | 张德志 | Outer tire of graphene tire |
| CN103374150A (en) * | 2012-04-24 | 2013-10-30 | 住友橡胶工业株式会社 | Rubber composition for tread and pneumatic tire using the same for tread |
| CN104672572A (en) * | 2013-11-28 | 2015-06-03 | 大连轮胎厂有限公司 | Composite material composition for tires |
Non-Patent Citations (1)
| Title |
|---|
| 石墨烯对载重轮胎胎面胶性能的影响;殷小波 等;《合成橡胶工业》;20140715;第37卷(第4期);第312-314页 * |
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| CN106336546A (en) | 2017-01-18 |
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