CN106987231A - Application of the heterogeneous couplings of zirconium phosphonate graphene oxide in friction material is prepared - Google Patents
Application of the heterogeneous couplings of zirconium phosphonate graphene oxide in friction material is prepared Download PDFInfo
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- C07F9/02—Phosphorus compounds
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Abstract
The present invention relates to application of the heterogeneous couplings of zirconium phosphonate graphene oxide in friction material is prepared.The synthesized heterogeneous couplings of two-dimensional nano filler zirconium phosphonate graphene oxide are added in friction material for 0.5~7.5% by mass percentage, by forming effective transfer membrane, and then wear rate effectively is reduced while coefficient of friction slightly declines, so as to improve the tribological property of automotive friction material.
Description
Technical field
The invention belongs to friction material field, it is related to the heterogeneous couplings of zirconium phosphonate graphene oxide and is preparing friction material
Application in material.
Background technology
The automotive friction material of high comprehensive performance is researched and developed, is the direction that present friction field is continued to develop.Friction catch
Material, it is usually a kind of heterogeneous composite material being made up of matrix material, reinforcing material, filler mixing.Wherein filler is to rub
One of three big components of material are wiped, including increases and rubs and antifriction filler etc., its main function is the fretting wear to friction material
Performance carries out many regulations.Traditional increasing rubs filler typically with certain hardness and shear strength, can make friction material
Material products have good friction factor.In recent years nano-particle because its size it is small, specific surface area is big and shows and conventional grain
The completely different physics of son and chemical property, it is all quite varied in the application of every field, so also causing in tribological field
Very high concern.Because size is small, nano-particle can substantially reduce the abrasive wear that hard filler is produced to flour milling；And because
The surface atom of nano-particle is more, and atom active is big, the generation of transfer membrane in friction process can be effectively facilitated, so as to improve base
The tribological property of body.At present, nano-particle is widely studied as a kind of new packing in friction material field.Phenolic aldehyde
Resin, as a kind of most widely used friction material resin matrix, is the primary study neck of nano-filler modified friction material
Domain.
Discovery is modified with nano silicon to phenolic resin in research in recent years, and to its high temperature ablation performance
It is tested, as a result shows that the resin after nano-silicon dioxide modified has higher resistance to ablation than traditional phenolic resin
Performance；With the layered nano silicate of different content, clay is modified to phenolic resin, and result of the test shows that nanoclay changes
Resin satisfactory mechanical property after property, and a certain degree of peeling can be reduced in wear process；Use nanometer Ti02Prepare
The nano-filled composite materials of phenolic resin, and its wearability and corrosion resistance studied, test result indicates that, nanometer
Ti02The wearability and friction factor of phenolic coating can be improved.There is increasing research work to concentrate on friction at present
It is largely focused in the research of Nano filling in material, but current research and individually adds a kind of Nano filling, in blending heat
It is especially in the majority to study zero-dimension nano filler in the molding mode of pressure.In two-dimensional nano surface side filler, the most of exploration are to make
In-situ polymerization modification is carried out to resin matrix with graphene and its derivative, this is due to the special form of graphite oxide alkenes material
The features such as state and Nano filling easily polymerize by way of blending so that improve the friction and wear behavior of automotive friction material
Become difficult.The mode being modified compared to in-situ polymerization, the mode of blending is clearly easily to be applied to actual production.Except this
Outside, the general individually addition in the formula of automotive friction material of these Nano fillings, or form addition is obtained with physical mixed,
The rare filler for probing into the heterogeneous coupling class being combined in the form of chemical Coupling.
Therefore the present invention has probed into a kind of novel lamellar two-dimensional nano filler-zirconium phosphonate oxidation regarding to the issue above
The heterogeneous couplings of graphene are as the filler of friction material, and by being blended, hot-forming mode prepares rubbed sample, and finding should
Sample reduces the coefficient of friction and wear rate of friction material by forming effective transfer membrane.
The content of the invention
In view of this, prepared it is an object of the invention to provide a kind of heterogeneous couplings of zirconium phosphonate graphene oxide
Application in friction material.
To reach above-mentioned purpose, the present invention provides following technical scheme：
1. application of the heterogeneous couplings of zirconium phosphonate graphene oxide in friction material is prepared.
Further, the heterogeneous couplings preparation method step of zirconium phosphonate graphene oxide is：
(1) ethephon (CEPHA),2-(chloroethyl) phosphonic acid is dissolved in frozen water, adds polyamines, KI and sodium hydroxide solution, it is anti-at 18~30 DEG C
Answer 100~200 hours, stand evaporative crystallization, then, be dried in vacuo to obtain organic phospho acid with alcohol recrystallization twice；
(2) by graphene oxide in water ultrasound 1h, add eight be hydrated zirconium oxychlorides, stir 1h~6h, add containing
The aqueous solution of machine phosphonic acid, the product of gained is filtered, distillation water washing 3 times, is dried in vacuo to obtain zirconium phosphonate graphene oxide
Heterogeneous couplings.
Further, ethephon (CEPHA),2-(chloroethyl) phosphonic acid mass concentration described in step (1) be 5.78g/L, the ethephon (CEPHA),2-(chloroethyl) phosphonic acid, polyamines, KI and
Sodium hydroxide ratio is 1:0.05~0.13:0.05~0.25:0.001~0.008 (g:mol:g:mol)；The sodium hydroxide is molten
Liquid concentration is 0.1mol/L~0.15mol/L.
Further, the polyamines is diethylenetriamine, ammoniacal liquor or TEPA.
Further, organic phospho acid molar concentration described in step (2) is 0.05~0.2mol/L, the graphene oxide matter
Amount concentration is 0.5~2.5g/L, and the organic phospho acid, eight hydration zirconium oxychlorides and graphene oxide ratio are 1:120~500:8~
35(mol:g:g)。
Further, it is dried in vacuo condition:24~48h is dried at 50 DEG C~60 DEG C.
Further, it is 0.5%~7.5% zirconium phosphonate graphene oxide containing mass percent in the friction material
Heterogeneous couplings.
Further, the friction material is following component by mass percentage：Phenolic resin 11%~20%, butyronitrile powder
2%~4%, mineral fibres 20%~29%, potassium titanate crystal whisker 15%~17%, graphite 4%~5%, aluminum oxide 1%~2%,
Barium sulfate 25%~35% and the heterogeneous couplings 0.5%~7.5% of zirconium phosphonate graphene oxide.
Further, it is that 1%~5% zirconium phosphonate graphene oxide is heterogeneous containing mass percent in the friction material
Couplings.
Further, the friction material preparation method is following steps：
(1) each component for taking mass percent sum to be 100% first is crushed with ball mill to be entered again with high speed disintegrator
Row mixing；
(2) mixture after step (1) is crushed is put into mould, 10MPa~20MPa is forced into, with 10 DEG C/min's
Programming rate is warming up to 160~200 DEG C, is forced into 25~35MPa, 20~40S of pressurize, deflation 5S~10S, repeats pressurize, lets out
Press gas 3~5 times, last 5~10min of pressurize is cooled to 18~25 DEG C of taking-up moulds, the demoulding；
(3) step (2) products therefrom carries out gradient increased temperature solidification, and 140 DEG C are incubated 2h~4h, 160 DEG C of insulation 2h~4h,
180 DEG C of insulation 2h~6h, obtain friction material.
The beneficial effects of the present invention are：A kind of two-dimentional heterogeneous couplings of zirconium phosphonate graphene oxide of stratiform are provided to make
For the filler of friction material, the filler nanometer characteristic and layer structure can reduce the shear term for constituting frictional force and can promote to turn
The formation of film is moved, so as to reduce the coefficient of friction and wear rate of friction material, the frictional behaviour of friction material is improved.
Brief description of the drawings
In order that the purpose of the present invention, technical scheme and beneficial effect are clearer, the present invention provides drawings described below and carried out
Explanation：
Fig. 1 is the friction material obtained by embodiment 1；
Fig. 2 is the friction material obtained by comparative example；
100 times of SEM figures at polishing scratch after friction material friction testings of the Fig. 3 obtained by comparative example；
200 times of SEM figures at polishing scratch after friction material friction testings of the Fig. 4 obtained by comparative example；
100 times of SEM figures at polishing scratch after friction material friction testings of the Fig. 5 obtained by embodiment 1；
200 times of SEM figures at polishing scratch after friction material friction testings of the Fig. 6 obtained by embodiment 1.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail.
Embodiment 1:
(1) preparation of the heterogeneous couplings of zirconium phosphonates graphene oxide：2.89g ethephon (CEPHA),2-(chloroethyl) phosphonic acid is dissolved in 500mL ice
In water, then 0.22mol diethylenetriamines, 0.3g KI, 160mL concentration are separately added into for 0.1mol/L NaOH solutions, at 18 DEG C
Lower reaction 120h, stands overnight rear evaporative crystallization, then, be put into vacuum drying chamber and dried at 60 DEG C with alcohol recrystallization twice
48h, obtains product 2-(2-(2-aminoethyl ammonia) ethyl ammonia) ethylphosphonic acid zirconium, referred to as (AE)3P；Again by 200mg graphite oxide
Alkene (GO) powder ultrasound 1h in 250mL water, it is rear to add the hydration zirconium oxychlorides of 4.8g eight (ZrOCl2·8H2O), 2h is stirred；Again
Will be dissolved with 4.2g (AE)3The P 150ml aqueous solution is added in the mixed solution of step, finally, and the product of gained is filtered, and is used
Distill water washing 3 times, 24h is dried in vacuo at 60 DEG C and obtains the heterogeneous couplings of zirconium phosphonate graphene oxide, the present embodiment is
Graphene oxide 2-(2-(2-aminoethyl ammonia) ethyl ammonia) ethylphosphonic acid zirconium (GO-Zr (AE)3P)。
(2) preparation of the friction material of the heterogeneous couplings of graphene oxides containing zirconium phosphonate：Phenol is taken by weight percent
Urea formaldehyde 11%, butyronitrile powder 4%, mineral fibres 28%, potassium titanate crystal whisker 15%, graphite 5%, aluminum oxide 2%, barium sulfate 30%
With the heterogeneous couplings of zirconium phosphonate graphene oxide 5%, crushed and be placed in after being mixed again with ball mill with high speed disintegrator
In hot pressing die, 10MPa is forced into, 170 DEG C are warming up to 10 DEG C/min programming rate, 30MPa, pressurize 180S is forced into,
Deflation 5S, repeats pressure release and deflates 3 times, specific number of times is regarded, depending on deflation situation, and deflation continues to during pressure release basic gas, and he overflows
Go out, last pressurize 5min, treat that temperature is down to the room temperature demoulding, the product after the demoulding is carried out in an oven solid after gradient increased temperature
Change, 140 DEG C of insulations 2h, 160 DEG C of insulations 2h, 180 DEG C of insulation 2h obtain rubbing for the heterogeneous couplings of graphene oxide containing zirconium phosphonate
Wipe material.
According to friction material made from the present embodiment, at room temperature with LSR-2M reciprocating friction Wear Testers, antithesis examination
Sample bearing steel ball diameter 4mm, fraction time 60min reciprocating frequences 100t/min, reciprocal diameter 10mm, dry friction loads 20N,
Friction and wear test is carried out, coefficient of friction (μ) and wear rate (v) are respectively 0.362 and 1.725 × 10-4mm3/Nm。
Fig. 1 is the friction material obtained by embodiment 1；Fig. 5 is that the friction material obtained by embodiment 1 passes through friction testing
100 times of SEM scheme at polishing scratch afterwards；Fig. 6 is friction material obtained by embodiment 1 200 times of SEM at polishing scratch after friction testing
Figure.From Fig. 5,6, organic phosphoric acid zirconium stannic oxide/graphene nano filler (GO- (AE) with the addition of3P its worn-out surface of sample)
Clearly more smooth, it can be seen that to have the formation of transfer membrane, this causes the abrasion resistance of material to have good lifting.Fig. 3 and
Fig. 4 is the sample polishing scratch rough surface for the comparative example for being not added with filler, inner stuffing exposure, so as to cause higher wear rate.
Embodiment 2:
(1) preparation of the heterogeneous couplings of zirconium phosphonates graphene oxide：2.89g ethephon (CEPHA),2-(chloroethyl) phosphonic acid is dissolved in 500mL ice
In water, then 0.22mol diethylenetriamines, 0.3gKI, 160mL concentration are separately added into for 0.1mol/LNaOH solution, at 18 DEG C
120h is reacted, rear evaporative crystallization is stood overnight.Finally the product of gained is recrystallized twice with alcohol, is put into vacuum drying chamber
48h is dried at 50 DEG C, obtains product (AE)3P.By 200mg graphene oxide (GO) powder in 250mL water it is ultrasonic
1h, it is rear to add the hydration zirconium oxychlorides of 4.8g eight (ZrOCl2·8H2O), 2h is stirred.By 4.2g (AE)3The P 150ml aqueous solution is added
Into the mixed solution of upper step.Finally, the product of gained is filtered, with water washing is distilled 3 times, 24h is dried in vacuo at 60 DEG C
Obtain the heterogeneous couplings of zirconium phosphonate graphene oxide.
(2) preparation of the friction material of the heterogeneous couplings of graphene oxides containing zirconium phosphonate：Phenol is taken by weight percent
Urea formaldehyde 11%, butyronitrile powder 4%, mineral fibres 28%, potassium titanate crystal whisker 15%, graphite 5%, aluminum oxide 2%, barium sulfate
32.5%, the heterogeneous couplings 2.5% of zirconium phosphonate graphene oxide are crushed with high speed disintegrator and mixed again with ball mill
After be placed in hot pressing die, be forced into 10MPa, 190 DEG C be warming up to 10 DEG C/min programming rate, be forced into 30MPa, pressurize
200S, deflation 5S, repeat pressure release and deflate 4 times, specific number of times is regarded, depending on deflation situation, deflate when continueing to pressure release substantially without gas
Body overflows, last pressurize 5min, treats that temperature is down to the room temperature demoulding, the sample after the demoulding is carried out into gradient increased temperature in an oven
Solidify afterwards, 140 DEG C of insulations 2h, 160 DEG C of insulations 2h, 180 DEG C of insulation 2h, obtain the heterogeneous couplings of graphene oxide containing zirconium phosphonate
Friction material.
The friction material being made according to the present embodiment, at room temperature with LSR-2M reciprocating friction Wear Testers, antithesis examination
Sample bearing steel ball diameter 4mm, fraction time 60min reciprocating frequences 100t/min, reciprocal diameter 10mm, dry friction loads 20N,
Friction and wear test is carried out, coefficient of friction (μ) and wear rate (v) are respectively 0.397 and 3.786 × 10-4mm3/Nm。
Embodiment 3：
(1) preparation of the heterogeneous couplings of zirconium phosphonates graphene oxide：2.89g ethephon (CEPHA),2-(chloroethyl) phosphonic acid is dissolved in 500mL ice
In water, then 0.22mol diethylenetriamines, 0.3gKI, 160mL concentration are separately added into for 0.1mol/L NaOH solutions, at 18 DEG C
120h is reacted, rear evaporative crystallization is stood overnight.Finally the product of gained is recrystallized twice with alcohol, is put into vacuum drying chamber
48h is dried at 60 DEG C, obtains product (AE)3P.By 200mg graphene oxide (GO) powder in 250mL water it is ultrasonic
1h, it is rear to add the hydration zirconium oxychlorides of 4.8g eight (ZrOCl2·8H2O), 2h is stirred.By 4.2g (AE)3The P 150ml aqueous solution is added
Into the mixed solution of upper step.Finally, the product of gained is filtered, with water washing is distilled 3 times, 24h is dried in vacuo at 60 DEG C
Obtain the heterogeneous couplings of zirconium phosphonate graphene oxide.
(2) preparation of the friction material of the heterogeneous couplings of graphene oxides containing zirconium phosphonate：Phenol is taken by weight percent
Urea formaldehyde 11%, butyronitrile powder 4%, mineral fibres 28%, potassium titanate crystal whisker 15%, graphite 5%, aluminum oxide 2%, barium sulfate
34.5%, the heterogeneous couplings 0.5% of zirconium phosphonate graphene oxide, after ball mill is mixed after being crushed with high speed disintegrator
It is placed in hot pressing die, is forced into 10MPa, 180 DEG C are warming up to 10 DEG C/min programming rate, is forced into 30MPa, pressurize
180S, deflation 5S, repeat pressure release and deflate 5 times, specific number of times is regarded, depending on deflation situation, deflate when continueing to pressure release substantially without gas
Body overflows, last pressurize 5min, treats that temperature is down to the room temperature demoulding, the sample after the demoulding is carried out into gradient increased temperature in an oven
Solidify afterwards, 140 DEG C of insulations 2h, 160 DEG C of insulations 2h, 180 DEG C of insulation 2h, obtain friction material.
The friction material being made according to the present embodiment, at room temperature with LSR-2M reciprocating friction Wear Testers, antithesis examination
Sample bearing steel ball diameter 4mm, fraction time 60min reciprocating frequences 100t/min, reciprocal diameter 10mm, dry friction loads 20N,
Friction and wear test is carried out, coefficient of friction (μ) and wear rate (v) are respectively 0.414 and 5.268 × 10-4mm3/Nm。
Embodiment 4：
(1) preparation of the heterogeneous couplings of zirconium phosphonates graphene oxide：2.89g ethephon (CEPHA),2-(chloroethyl) phosphonic acid is dissolved in 500mL ice
In water, then 0.34mol ammoniacal liquor, 0.2gKI and 160mL concentration are separately added into for 0.1mol/L NaOH solutions, reacted at 18 DEG C
120h, stands overnight rear evaporative crystallization.Finally the product of gained is recrystallized twice with alcohol, is put into vacuum drying chamber 60
48h is dried at DEG C, obtains product H3O3PCH2CH2NH2(abbreviation AEP).By 250mg graphene oxide (GO) powder in 250mL
Water in ultrasound 1h, it is rear to add the hydration zirconium oxychlorides of 6.8g eight (ZrOCl2·8H2O), 2h is stirred.2gAEP 120ml is water-soluble
Liquid is added in the mixed solution of step.Finally, the product of gained is filtered, with water washing is distilled 3 times, vacuum is done at 60 DEG C
Dry 24h obtains the heterogeneous couplings of zirconium phosphonate graphene oxide.
(2) preparation of the friction material of the heterogeneous couplings of graphene oxides containing zirconium phosphonate：Phenol is taken by weight percent
Urea formaldehyde 11%, butyronitrile powder 4%, mineral fibres 28%, potassium titanate crystal whisker 15%, graphite 5%, aluminum oxide 2%, barium sulfate
34.5%, the heterogeneous couplings 0.5% of zirconium phosphonate graphene oxide, after ball mill is mixed after being crushed with high speed disintegrator
It is placed in hot pressing die, is forced into 10MPa, 180 DEG C are warming up to 10 DEG C/min programming rate, is forced into 30MPa, pressurize
180S, deflation 5S, repeat pressure release and deflate 5 times, specific number of times is regarded, depending on deflation situation, deflate when continueing to pressure release substantially without gas
Body overflows, last pressurize 5min, treats that temperature is down to the room temperature demoulding, the sample after the demoulding is carried out into gradient increased temperature in an oven
Solidify afterwards, 140 DEG C of insulations 2h, 160 DEG C of insulations 2h, 180 DEG C of insulation 2h, obtain friction material.
The friction material being made according to the present embodiment, at room temperature with LSR-2M reciprocating friction Wear Testers, antithesis examination
Sample bearing steel ball diameter 4mm, fraction time 60min reciprocating frequences 100t/min, reciprocal diameter 10mm, dry friction loads 20N,
Friction and wear test is carried out, coefficient of friction (μ) and wear rate (v) are respectively 0.384 and 4.018 × 10-4mm3/Nm。
Embodiment 5：
(1) preparation of the heterogeneous couplings of zirconium phosphonates graphene oxide：2.89g ethephon (CEPHA),2-(chloroethyl) phosphonic acid is dissolved in 500mL ice
In water, then 0.28mol TEPAs, 0.2gKI, 200mL concentration are separately added into for 0.1mol/L NaOH solutions, at 18 DEG C
120h is reacted, rear evaporative crystallization is stood overnight.Finally the product of gained is recrystallized twice with alcohol, is put into vacuum drying chamber
48h is dried at 60 DEG C, obtains product (AE)5P.By 500mg graphene oxide (GO) powder in 250mL water it is ultrasonic
1h, it is rear to add the hydration zirconium oxychlorides of 4.8g eight (ZrOCl28H2O), 2h is stirred.Will be dissolved with 6g (AE)5The P 150ml aqueous solution adds
Enter into the mixed solution of upper step.Finally, the product of gained is filtered, with water washing is distilled 3 times, be dried in vacuo at 60 DEG C
24h obtains the heterogeneous couplings of zirconium phosphonate graphene oxide.
(2) preparation of the friction material of the heterogeneous couplings of graphene oxides containing zirconium phosphonate：Phenol is taken by weight percent
Urea formaldehyde 11%, butyronitrile powder 4%, mineral fibres 28%, potassium titanate crystal whisker 15%, graphite 5%, aluminum oxide 2%, barium sulfate
34.5%, the heterogeneous couplings 0.5% of zirconium phosphonate graphene oxide, after ball mill is mixed after being crushed with high speed disintegrator
It is placed in hot pressing die, is forced into 10MPa, 180 DEG C are warming up to 10 DEG C/min programming rate, is forced into 30MPa, pressurize
180S, deflation 5S, repeat pressure release and deflate 5 times, specific number of times is regarded, depending on deflation situation, deflate when continueing to pressure release substantially without gas
Body overflows, last pressurize 5min, treats that temperature is down to the room temperature demoulding, the sample after the demoulding is carried out into gradient increased temperature in an oven
Solidify afterwards, 140 DEG C of insulations 2h, 160 DEG C of insulations 2h, 180 DEG C of insulation 2h, obtain friction material.
The friction material being made according to the present embodiment, at room temperature with LSR-2M reciprocating friction Wear Testers, antithesis examination
Sample bearing steel ball diameter 4mm, fraction time 60min reciprocating frequences 100t/min, reciprocal diameter 10mm, dry friction loads 20N,
Friction and wear test is carried out, coefficient of friction (μ) and wear rate (v) are respectively 3.92 and 2.976 × 10-4mm3/Nm。
The heterogeneous couplings molecular structural formula of zirconium phosphonate graphene oxide is as shown in formula I：
Wherein n values are 1-9 arbitrary integers, a1Represent graphene oxide layer planar structure, a2Represent organic phosphoric acid sheeting
Layer plane structure.
Comparative example：
Phenolic resin 11%, butyronitrile powder 4%, mineral fibres 29%, potassium titanate crystal whisker 15%, graphite are taken by weight percent
5%, aluminum oxide 2%, barium sulfate 35%, ball mill is placed in hot pressing die after being mixed after being crushed with high speed disintegrator, plus
10MPa is depressed into, 170 DEG C are warming up to 10 DEG C/min programming rate, 30MPa, pressurize 180S, deflation 5S is forced into, repetition is let out
Press gas 3 times, specific number of times is regarded, depending on deflation situation, deflate when continueing to pressure release substantially without gas overflowing, last pressurize
5min, treats that temperature is down to the room temperature demoulding, and the sample after the demoulding is carried out into gradient increased temperature solidify afterwards, 140 DEG C of guarantors in an oven
Warm 2h, 160 DEG C of insulations 2h, 180 DEG C of insulation 2h, obtains friction material.
Fig. 2 is the friction material obtained by comparative example；Polishing scratch after friction material friction testings of the Fig. 3 obtained by comparative example
100 times of place SEM figures；200 times of SEM figures at polishing scratch after friction material friction testings of the Fig. 4 obtained by comparative example.
The friction material being made according to the present embodiment, at room temperature with LSR-2M reciprocating friction Wear Testers, antithesis examination
Sample：Bearing steel ball diameter 4mm, fraction time 60min reciprocating frequences 100t/min, reciprocal diameter 10mm, dry friction loads 20N,
Friction and wear test is carried out, coefficient of friction (μ) and wear rate (v) are respectively 0.475 and 9.778 × 10-4mm3/Nm。
The coefficient of friction (μ) and wear rate (v) of friction material and comparative example gained friction material as obtained by embodiment 1-5
Compare, add the heterogeneous couplings gained friction material of zirconium phosphonate graphene oxide and ground while coefficient of friction slightly declines
Loss rate is effectively reduced, so as to improve the frictional behaviour of friction material.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical
Cross above preferred embodiment the present invention is described in detail, it is to be understood by those skilled in the art that can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (10)
1. application of the heterogeneous couplings of zirconium phosphonate graphene oxide in friction material is prepared.
2. application of the heterogeneous couplings of zirconium phosphonate graphene oxide in friction material is prepared according to claim 1,
Characterized in that, the heterogeneous couplings preparation method step of zirconium phosphonate graphene oxide is：
(1) ethephon (CEPHA),2-(chloroethyl) phosphonic acid is dissolved in frozen water, adds polyamines, KI and sodium hydroxide solution, 100 are reacted at 18~30 DEG C
~200 hours, evaporative crystallization is stood, then, be dried in vacuo to obtain organic phospho acid with alcohol recrystallization twice；
(2) by graphene oxide in water ultrasound 1h, add eight be hydrated zirconium oxychlorides, stir 1h~6h, add containing organic phosphine
The aqueous solution of acid, the product of gained is filtered, distillation water washing 3 times, be dried in vacuo zirconium phosphonate graphene oxide is heterogeneous
Couplings.
3. application of the heterogeneous couplings of zirconium phosphonate graphene oxide in friction material is prepared according to claim 2,
Characterized in that, ethephon (CEPHA),2-(chloroethyl) phosphonic acid mass concentration described in step (1) is 5.78g/L, the ethephon (CEPHA),2-(chloroethyl) phosphonic acid, polyamines, KI and hydrogen-oxygen
It is 1 to change sodium ratio:0.05~0.13:0.05~0.25:0.001~0.008 (g:mol:g:mol)；The sodium hydroxide solution is dense
Spend for 0.1mol/L~0.15mol/L.
4. application of the heterogeneous couplings of zirconium phosphonate graphene oxide in friction material is prepared according to claim 2,
Characterized in that, the polyamines is diethylenetriamine, ammoniacal liquor or TEPA.
5. application of the heterogeneous couplings of zirconium phosphonate graphene oxide in friction material is prepared according to claim 2,
Characterized in that, organic phospho acid molar concentration described in step (2) is 0.05~0.2mol/L, the graphene oxide quality is dense
Spend for 0.5~2.5g/L, the organic phospho acid, eight hydration zirconium oxychlorides and graphene oxide ratio are 1:120~500:8~35
(mol:g:g)。
6. application of the heterogeneous couplings of zirconium phosphonate graphene oxide in friction material is prepared according to claim 2,
Characterized in that, vacuum drying condition:24~48h is dried at 50 DEG C~60 DEG C.
7. application of the heterogeneous couplings of zirconium phosphonate graphene oxide in friction material is prepared described in claim 1, it is special
Levy and be, it is the heterogeneous coupling of 0.5~7.5% zirconium phosphonate graphene oxide that mass percent is contained in the friction material
Thing.
8. application of the heterogeneous couplings of zirconium phosphonate graphene oxide in friction material is prepared according to claim 7,
Characterized in that, the friction material is following component by mass percentage：Phenolic resin 11%~20%, butyronitrile powder 2%~
4%, mineral fibres 20%~29%, potassium titanate crystal whisker 15%~17%, graphite 4%~5%, aluminum oxide 1%~2%, sulfuric acid
Barium 25%~35% and the heterogeneous couplings 0.5~7.5% of zirconium phosphonate graphene oxide.
9. application of the heterogeneous couplings of zirconium phosphonate graphene oxide in friction material is prepared according to claim 7,
Characterized in that, it is the heterogeneous coupling of 1%~5% zirconium phosphonate graphene oxide to contain mass percent in the friction material
Thing.
10. any one of the claim 7~9 heterogeneous couplings of zirconium phosphonate graphene oxide are in friction material is prepared
Using, it is characterised in that the friction material preparation method is following steps：
(1) each component for taking mass percent sum to be 100% is first crushed with high speed disintegrator to be mixed with ball mill again
Close；
(2) mixture after step (1) is crushed is put into mould, 10MPa~20MPa is forced into, with 10 DEG C/min heating
Speed is warming up to 160~200 DEG C, is forced into 25~35MPa, 20~40S of pressurize, deflation 5S~10S, repeats pressurize, pressure release and puts
Gas 3~5 times, last 5~10min of pressurize is cooled to 18~25 DEG C of taking-up moulds, the demoulding；
(3) step (2) products therefrom carries out gradient increased temperature solidification, and 140 DEG C are incubated 2h~4h, and 160 DEG C are incubated 2h~4h, 180 DEG C
2h~6h is incubated, friction material is obtained.
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| CN110821994A (en) * | 2019-10-22 | 2020-02-21 | 泰明顿摩擦材料技术(上海)有限公司 | High-performance copper-free automobile brake pad and preparation method thereof |
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