CN105526287A - Preparation method for nano ceramic fiber/phenolic resin composite frictional material - Google Patents

Abstract

The invention relates to a preparation method for a nano ceramic fiber/phenolic resin composite frictional material, and belongs to the field of preparation of the frictional material. In order to solve the problems that in the using process of the frictional material at present, the high temperature resistance overall performance is poor, and the temperature of the frictional material and the mating surface is too high under the effects of high speed and high pressure, so that braking can not be achieved, a polymeric pecursor solution is prepared through zirconium oxychloride octahydrate and boric acid, then electrostatic spinning is carried out, and a nano ceramic material is prepared through calcination; then the nano ceramic material is modified and is subject to group grafting; and while phenolic resin is prepared, a nano fiber material is added for modification. According to the preparation method, ceramic nano fibers are modified into the frictional material, and the glass transition temperature can reach 250 DEG C to 260 DEG C; and the frictional material is prepared from the phenolic resin and the ceramic nano fibers, the cost is low, and operation is easy.

Description

The preparation method of a kind of nano ceramic fibers/phenolic resin composite friction material

Technical field

The present invention relates to the preparation method of a kind of nano ceramic fibers/phenolic resin composite friction material, belong to friction material preparation field.

Background technique

Friction material is that one is applied on dynamic power machine, rubbing action is relied on to perform the component materials of braking and transmission agency, it is commonly called as brake block mainly for the manufacture of brake facing and clutch surface is commonly called as clutch plate, and brake block is used for braking, and clutch is used for transmission.The various vehicles of any machinery and motion, all must have braking device.Friction material is the critical component on this braking device.It enables machinery and the safe and reliable work of various motor vehicle, is widely used so friction material is one, material very crucial again.Braking is one of important behavior of vehicle operating, and current great majority take friction catch, and the frictional force namely produced by relative movement between friction plate and brake disc, as braking force, makes moving object safety brake.Therefore braking system is to the Security of vehicle, travelling comfort, and energy consumption and pollution etc. have significant impact, and the performance and structure of the friction pair wherein in braking system is the basic influence factor of riding comfort, durability particularly Security.

Current friction material is high temperature resistant, and combination property is poor.Under high speed and High Pressure, the temperature on friction material and antithesis surface can up to 800 ~ 1000 DEG C, therefore require very high to the high-temperature comprehensive property of friction material, and for Polymers friction material, due to the resistance to heat of matrix organic material and heat-conducting property lower, so need a kind of can the inorganic material of quick conductive and heat radiation to carry out modification necessary.

Summary of the invention

Technical problem to be solved by this invention: poor for high temperature resistant combination property in current friction material using process, under high speed and High Pressure, the temperature on friction material and antithesis surface is too high, cause the problem that cannot brake, provide a kind of by eight hydration zirconium oxychlorides and boric acid are prepared precursor solution, electrostatic spinning is also calcined and is prepared nano ceramic material subsequently, subsequently to its modify and graft group, while preparing phenolic resin, nano-fiber material is added and wherein carries out modification, increase substantially the heat radiation of its friction material and resistance to heat.

For solving the problems of the technologies described above, the present invention adopts technological scheme as described below to be:

(1) at 20 ~ 30 DEG C, by solid-liquid mass ratio 1:10, by in eight hydration zirconyl chloride solution distilled water, be uniformly mixed 10 ~ 15min, be prepared into zirconyl chloride solution, be the BAS mass ratio 15:1 of 10% subsequently by zirconyl chloride solution and mass fraction, BAS is dropped in zirconyl chloride solution, be uniformly mixed 25 ~ 30min, to be mixed complete after, continue the citric acid solution dripping the above-mentioned sucrose solution of solution gross mass 5% and the 0.85mol/L of 7%, to be uniformly mixed and after reacting 10 ~ 12h, pH to 4 ~ 6 are regulated with the ammonia spirit that mass concentration is 10%, be prepared into precursor solution,

(2) be 2:3 by polyvinyl alcohol and precursor solution mass ratio, polyvinyl alcohol is slowly added in precursor solution, after stirring reaction 40 ~ 48h, at 55 ~ 60 DEG C, vacuum defoamation concentrates 3h, standing and defoaming process 10 ~ 12h again, be prepared into ceramic fiber spinning solution, subsequently ceramic fiber spinning solution is injected the injector that nozzle is housed, nozzle diameter is 1mm, adjustment nozzle and horizontal plane angle are 10 °, arranging voltage is 30kV, solidification distance is 12 ~ 15cm, at 20 ~ 25 DEG C, spinning is carried out when relative moisture is 50 ~ 60%, collect and be placed in tube furnace and carry out cracking, arranging cracking temperature is 1580 ~ 1600 DEG C, 20 ~ 30 DEG C are cooled to after insulation 2h, be prepared into nano ceramic fibers,

(3) nano ceramic fibers of above-mentioned preparation is placed in the there-necked flask of 250mL, dry 2 ~ 3h under 120 DEG C of vacuum, after temperature is down to 50 ~ 60 DEG C, after rubber seal is good, by 10% of gross mass, 3-glycydoxy trimethoxysilane coupling agent is added in there-necked flask, subsequently at 200 ~ 300W ultrasonic wave added vibration, 2 ~ 3h, and to its heating stirring and refluxing reaction 5 ~ 6h that heats up, subsequently it filtered and use toluene and acetone to wash 2 ~ 3 times respectively, and dry 6 ~ 8h at being placed on 80 ~ 90 DEG C, be prepared into modified Nano ceramic fiber;

(4) count by weight, choose the phenol of 35 ~ 55 parts, the formaldehyde of 15 ~ 20 parts, the oxalic acid of the modified Nano ceramic fiber of 10 ~ 15 parts of above-mentioned preparations and 20 ~ 30 parts is placed in the there-necked flask of 250mL, under 600 ~ 800r/min, stirring is warming up to 60 ~ 80 DEG C, insulation reaction 3 ~ 4h, after question response completes, continue to be warming up to 150 DEG C, subsequently processed is vacuumized to it, after moisture content is removed, continue be heated to 200 DEG C and react 1 ~ 2h, stop heating and leaving standstill subsequently being cooled to 20 ~ 30 DEG C, a kind of nano ceramic fibers/phenolic resin composite friction material can be prepared into.

Application process of the present invention is: will be prepared into a kind of nano ceramic fibers/phenolic resin composite friction material and pulverize, then curing agent, curing accelerator, frictional behaviour modifier, mineral filler etc. are added, all hook mixing, open auxiliary refining machine is utilized to carry out mixing, rod temperature 110 DEG C before controlling, rear roll temperature 120 DEG C, to its roller refining 10min, then pulverized, inject mould, be prepared into clutch friction material.

The present invention is compared with additive method, and Advantageous Effects is:

(1) the present invention is by ceramic nanofibers modified friction material, and glass transition temperature can reach 250 ~ 260 DEG C;

(2) be prepared by phenolic resin and ceramic nanofibers, cost is low, easy to operate.

Embodiment

First at 20 ~ 30 DEG C, by solid-liquid mass ratio 1:10, eight hydration zirconium oxychlorides are dissolved in distilled water, be uniformly mixed 10 ~ 15min, be prepared into zirconyl chloride solution, be the BAS mass ratio 15:1 of 10% subsequently by zirconyl chloride solution and mass fraction, BAS is dropped in zirconyl chloride solution, be uniformly mixed 25 ~ 30min, to be mixed complete after, continue the citric acid solution dripping the above-mentioned sucrose solution of solution gross mass 5% and the 0.85mol/L of 7%, to be uniformly mixed and after reacting 10 ~ 12h, pH to 4 ~ 6 are regulated with the ammonia spirit that mass concentration is 10%, be prepared into precursor solution, be 2:3 by polyvinyl alcohol and precursor solution mass ratio, polyvinyl alcohol is slowly added in precursor solution, after stirring reaction 40 ~ 48h, at 55 ~ 60 DEG C, vacuum defoamation concentrates 3h, standing and defoaming process 10 ~ 12h again, be prepared into ceramic fiber spinning solution, subsequently ceramic fiber spinning solution is injected the injector that nozzle is housed, nozzle diameter is 1mm, adjustment nozzle and horizontal plane angle are 10 °, arranging voltage is 30kV, solidification distance is 12 ~ 15cm, at 20 ~ 25 DEG C, spinning is carried out when relative moisture is 50 ~ 60%, collect and be placed in tube furnace and carry out cracking, arranging cracking temperature is 1580 ~ 1600 DEG C, 20 ~ 30 DEG C are cooled to after insulation 2h, be prepared into nano ceramic fibers, the nano ceramic fibers of above-mentioned preparation is placed in the there-necked flask of 250mL, dry 2 ~ 3h under 120 DEG C of vacuum, after temperature is down to 50 ~ 60 DEG C, after rubber seal is good, by 10% of gross mass, 3-glycydoxy trimethoxysilane coupling agent is added in there-necked flask, subsequently at 200 ~ 300W ultrasonic wave added vibration, 2 ~ 3h, and to its heating stirring and refluxing reaction 5 ~ 6h that heats up, subsequently it filtered and use toluene and acetone to wash 2 ~ 3 times respectively, and dry 6 ~ 8h at being placed on 80 ~ 90 DEG C, be prepared into modified Nano ceramic fiber, count by weight, choose the phenol of 35 ~ 55 parts, the formaldehyde of 15 ~ 20 parts, the oxalic acid of the modified Nano ceramic fiber of 10 ~ 15 parts of above-mentioned preparations and 20 ~ 30 parts is placed in the there-necked flask of 250mL, under 600 ~ 800r/min, stirring is warming up to 60 ~ 80 DEG C, insulation reaction 3 ~ 4h, after question response completes, continue to be warming up to 150 DEG C, subsequently processed is vacuumized to it, after moisture content is removed, continue be heated to 200 DEG C and react 1 ~ 2h, stop heating and leaving standstill subsequently being cooled to 20 ~ 30 DEG C, a kind of nano ceramic fibers/phenolic resin composite friction material can be prepared into.

Example 1

First at 20 DEG C, by solid-liquid mass ratio 1:10, eight hydration zirconium oxychlorides are dissolved in distilled water, be uniformly mixed 10min, be prepared into zirconyl chloride solution, be the BAS mass ratio 15:1 of 10% subsequently by zirconyl chloride solution and mass fraction, BAS is dropped in zirconyl chloride solution, be uniformly mixed 25min, to be mixed complete after, continue the citric acid solution dripping the above-mentioned sucrose solution of solution gross mass 5% and the 0.85mol/L of 7%, to be uniformly mixed and after reacting 10h, pH to 4 is regulated with the ammonia spirit that mass concentration is 10%, be prepared into precursor solution, be 2:3 by polyvinyl alcohol and precursor solution mass ratio, polyvinyl alcohol is slowly added in precursor solution, after stirring reaction 40h, at 55 DEG C, vacuum defoamation concentrates 3h, standing and defoaming process 10h again, be prepared into ceramic fiber spinning solution, subsequently ceramic fiber spinning solution is injected the injector that nozzle is housed, nozzle diameter is 1mm, adjustment nozzle and horizontal plane angle are 10 °, arranging voltage is 30kV, solidification distance is 12cm, at 20 DEG C, spinning is carried out when relative moisture is 50%, collect and be placed in tube furnace and carry out cracking, arranging cracking temperature is 1580 DEG C, 20 DEG C are cooled to after insulation 2h, be prepared into nano ceramic fibers, the nano ceramic fibers of above-mentioned preparation is placed in the there-necked flask of 250mL, dry 2h under 120 DEG C of vacuum, after temperature is down to 50 DEG C, after rubber seal is good, by 10% of gross mass, 3-glycydoxy trimethoxysilane coupling agent is added in there-necked flask, subsequently at 200W ultrasonic wave added vibration 2h, and to its heating stirring and refluxing reaction 5h that heats up, subsequently it filtered and use toluene and acetone to wash 2 times respectively, and dry 6h at being placed on 80 DEG C, be prepared into modified Nano ceramic fiber, count by weight, choose the phenol of 35 parts, the formaldehyde of 20 parts, the modified Nano ceramic fiber of 15 parts of above-mentioned preparations and 30 parts oxalic acid be placed in the there-necked flask of 250mL, under 600r/min, stirring is warming up to 60 DEG C, insulation reaction 3h, after question response completes, continue to be warming up to 150 DEG C, subsequently processed is vacuumized to it, after moisture content is removed, continue be heated to 200 DEG C and react 1h, stop heating and leaving standstill subsequently being cooled to 20 DEG C, a kind of nano ceramic fibers/phenolic resin composite friction material can be prepared into.

A kind of nano ceramic fibers/phenolic resin composite friction material will be prepared into pulverize, and then add curing agent, curing accelerator, frictional behaviour modifier, mineral filler etc., all hook mixing.Utilize open auxiliary refining machine to carry out mixing, rod temperature 110 DEG C before controlling, rear roll temperature 120 DEG C, to its roller refining 10min, then pulverized, inject mould, be prepared into clutch friction material.

Example 2

First at 25 DEG C, by solid-liquid mass ratio 1:10, eight hydration zirconium oxychlorides are dissolved in distilled water, be uniformly mixed 12min, be prepared into zirconyl chloride solution, be the BAS mass ratio 15:1 of 10% subsequently by zirconyl chloride solution and mass fraction, BAS is dropped in zirconyl chloride solution, be uniformly mixed 27min, to be mixed complete after, continue the citric acid solution dripping the above-mentioned sucrose solution of solution gross mass 5% and the 0.85mol/L of 7%, to be uniformly mixed and after reacting 11h, pH to 5 is regulated with the ammonia spirit that mass concentration is 10%, be prepared into precursor solution, be 2:3 by polyvinyl alcohol and precursor solution mass ratio, polyvinyl alcohol is slowly added in precursor solution, after stirring reaction 44h, at 58 DEG C, vacuum defoamation concentrates 3h, standing and defoaming process 11h again, be prepared into ceramic fiber spinning solution, subsequently ceramic fiber spinning solution is injected the injector that nozzle is housed, nozzle diameter is 1mm, adjustment nozzle and horizontal plane angle are 10 °, arranging voltage is 30kV, solidification distance is 13cm, at 22 DEG C, spinning is carried out when relative moisture is 55%, collect and be placed in tube furnace and carry out cracking, arranging cracking temperature is 1590 DEG C, 25 DEG C are cooled to after insulation 2h, be prepared into nano ceramic fibers, the nano ceramic fibers of above-mentioned preparation is placed in the there-necked flask of 250mL, dry 2.5h under 120 DEG C of vacuum, after temperature is down to 55 DEG C, after rubber seal is good, by 10% of gross mass, 3-glycydoxy trimethoxysilane coupling agent is added in there-necked flask, subsequently at 250W ultrasonic wave added vibration 2.5h, and to its heating stirring and refluxing reaction 5.5h that heats up, subsequently it filtered and use toluene and acetone to wash 2.5 times respectively, and dry 7h at being placed on 85 DEG C, be prepared into modified Nano ceramic fiber, count by weight, choose the phenol of 40 parts, the formaldehyde of 15 parts, the modified Nano ceramic fiber of 15 parts of above-mentioned preparations and 30 parts oxalic acid be placed in the there-necked flask of 250mL, under 700r/min, stirring is warming up to 70 DEG C, insulation reaction 3.5, after question response completes, continue to be warming up to 150 DEG C, subsequently processed is vacuumized to it, after moisture content is removed, continue be heated to 200 DEG C and react 1.5h, stop heating and leaving standstill subsequently being cooled to 25 DEG C, a kind of nano ceramic fibers/phenolic resin composite friction material can be prepared into.

A kind of nano ceramic fibers/phenolic resin composite friction material will be prepared into pulverize, and then add curing agent, curing accelerator, frictional behaviour modifier, mineral filler etc., all hook mixing.Utilize open auxiliary refining machine to carry out mixing, rod temperature 110 DEG C before controlling, rear roll temperature 120 DEG C, to its roller refining 10min, then pulverized, inject mould, be prepared into clutch friction material.

Example 3

First at 30 DEG C, by solid-liquid mass ratio 1:10, eight hydration zirconium oxychlorides are dissolved in distilled water, be uniformly mixed 15min, be prepared into zirconyl chloride solution, be the BAS mass ratio 15:1 of 10% subsequently by zirconyl chloride solution and mass fraction, BAS is dropped in zirconyl chloride solution, be uniformly mixed 30min, to be mixed complete after, continue the citric acid solution dripping the above-mentioned sucrose solution of solution gross mass 5% and the 0.85mol/L of 7%, to be uniformly mixed and after reacting 12h, pH to 6 is regulated with the ammonia spirit that mass concentration is 10%, be prepared into precursor solution, be 2:3 by polyvinyl alcohol and precursor solution mass ratio, polyvinyl alcohol is slowly added in precursor solution, after stirring reaction 48h, at 60 DEG C, vacuum defoamation concentrates 3h, standing and defoaming process 12h again, be prepared into ceramic fiber spinning solution, subsequently ceramic fiber spinning solution is injected the injector that nozzle is housed, nozzle diameter is 1mm, adjustment nozzle and horizontal plane angle are 10 °, arranging voltage is 30kV, solidification distance is 15cm, at 25 DEG C, spinning is carried out when relative moisture is 60%, collect and be placed in tube furnace and carry out cracking, arranging cracking temperature is 1600 DEG C, 30 DEG C are cooled to after insulation 2h, be prepared into nano ceramic fibers, the nano ceramic fibers of above-mentioned preparation is placed in the there-necked flask of 250mL, dry 3h under 120 DEG C of vacuum, after temperature is down to 60 DEG C, after rubber seal is good, by 10% of gross mass, 3-glycydoxy trimethoxysilane coupling agent is added in there-necked flask, subsequently at 300W ultrasonic wave added vibration 3h, and to its heating stirring and refluxing reaction 6h that heats up, subsequently it filtered and use toluene and acetone to wash 3 times respectively, and dry 8h at being placed on 90 DEG C, be prepared into modified Nano ceramic fiber, count by weight, choose the phenol of 55 parts, the formaldehyde of 15 parts, the modified Nano ceramic fiber of 10 parts of above-mentioned preparations and 20 parts oxalic acid be placed in the there-necked flask of 250mL, under 800r/min, stirring is warming up to 80 DEG C, insulation reaction 4h, after question response completes, continue to be warming up to 150 DEG C, subsequently processed is vacuumized to it, after moisture content is removed, continue be heated to 200 DEG C and react 2h, stop heating and leaving standstill subsequently being cooled to 30 DEG C, a kind of nano ceramic fibers/phenolic resin composite friction material can be prepared into.

A kind of nano ceramic fibers/phenolic resin composite friction material will be prepared into pulverize, and then add curing agent, curing accelerator, frictional behaviour modifier, mineral filler etc., all hook mixing.Utilize open auxiliary refining machine to carry out mixing, rod temperature 110 DEG C before controlling, rear roll temperature 120 DEG C, to its roller refining 10min, then pulverized, inject mould, be prepared into clutch friction material.

Claims (1)

1. a preparation method for nano ceramic fibers/phenolic resin composite friction material, is characterized in that concrete preparation process is:

(1) at 20 ~ 30 DEG C, by solid-liquid mass ratio 1:10, eight hydration zirconium oxychlorides are dissolved in distilled water, be uniformly mixed 10 ~ 15min, be prepared into zirconyl chloride solution, be the BAS mass ratio 15:1 of 10% subsequently by zirconyl chloride solution and mass fraction, BAS is dropped in zirconyl chloride solution, be uniformly mixed 25 ~ 30min, to be mixed complete after, continue the citric acid solution dripping the above-mentioned sucrose solution of solution gross mass 5% and the 0.85mol/L of 7%, to be uniformly mixed and after reacting 10 ~ 12h, pH to 4 ~ 6 are regulated with the ammonia spirit that mass concentration is 10%, be prepared into precursor solution,

(2) be 2:3 by polyvinyl alcohol and precursor solution mass ratio, polyvinyl alcohol is slowly added in precursor solution, after stirring reaction 40 ~ 48h, at 55 ~ 60 DEG C, vacuum defoamation concentrates 3h, standing and defoaming process 10 ~ 12h again, be prepared into ceramic fiber spinning solution, subsequently ceramic fiber spinning solution is injected the injector that nozzle is housed, nozzle diameter is 1mm, adjustment nozzle and horizontal plane angle are 10 °, arranging voltage is 30kV, solidification distance is 12 ~ 15cm, at 20 ~ 25 DEG C, spinning is carried out when relative moisture is 50 ~ 60%, collect and be placed in tube furnace and carry out cracking, arranging cracking temperature is 1580 ~ 1600 DEG C, 20 ~ 30 DEG C are cooled to after insulation 2h, be prepared into nano ceramic fibers,

(3) nano ceramic fibers of above-mentioned preparation is placed in the there-necked flask of 250mL, dry 2 ~ 3h under 120 DEG C of vacuum, after temperature is down to 50 ~ 60 DEG C, after rubber seal is good, by 10% of gross mass, 3-glycydoxy trimethoxysilane coupling agent is added in there-necked flask, subsequently at 200 ~ 300W ultrasonic wave added vibration, 2 ~ 3h, and to its heating stirring and refluxing reaction 5 ~ 6h that heats up, subsequently it filtered and use toluene and acetone to wash 2 ~ 3 times respectively, and dry 6 ~ 8h at being placed on 80 ~ 90 DEG C, be prepared into modified Nano ceramic fiber;

(4) count by weight, choose the phenol of 35 ~ 55 parts, the formaldehyde of 15 ~ 20 parts, the oxalic acid of the modified Nano ceramic fiber of 10 ~ 15 parts of above-mentioned preparations and 20 ~ 30 parts is placed in the there-necked flask of 250mL, under 600 ~ 800r/min, stirring is warming up to 60 ~ 80 DEG C, insulation reaction 3 ~ 4h, after question response completes, continue to be warming up to 150 DEG C, subsequently processed is vacuumized to it, after moisture content is removed, continue be heated to 200 DEG C and react 1 ~ 2h, stop heating and leaving standstill subsequently being cooled to 20 ~ 30 DEG C, a kind of nano ceramic fibers/phenolic resin composite friction material can be prepared into.