CN101629016A - Preparation method of nano CaCO3/polyimide composite - Google Patents
Preparation method of nano CaCO3/polyimide composite Download PDFInfo
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- CN101629016A CN101629016A CN200910055616A CN200910055616A CN101629016A CN 101629016 A CN101629016 A CN 101629016A CN 200910055616 A CN200910055616 A CN 200910055616A CN 200910055616 A CN200910055616 A CN 200910055616A CN 101629016 A CN101629016 A CN 101629016A
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- nanometer caco
- polyimide
- nanometer
- rare earth
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Abstract
The invention relates to a preparation method of a nano CaCO3/polyimide composite, comprising the following steps: first adopting a rare earth modifier at room temperature to carry out surface modification treatment on the nano CaCO3, then placing the treated nano CaCO3 into a ball mill to undergo ball milling, mechanically blending the nano CaCO3 undergoing ball milling with polyimide powder, controlling the weight percent of the nano CaCO3 to be 0.8-8% of the blended powder, then placing the blended powder into a die to be formed by pressing and preparing the composite through high temperature sintering, wherein, the rare earth modifier is prepared by rare earth compounds, ethanol, ethylene diamine tetraacetic acid, ammonium chloride, nitric acid and urea. The method is simple in process, low in cost and free of environmental pollution, and the prepared rare earth modified nano CaCO3/polyimide composite enjoys good mechanical property and tribological property.
Description
Technical field
The present invention relates to a kind of composite material and preparation method thereof, relate in particular to a kind of rare earth modified nano CaCO
3/ composite polyimide material preparation method adopts through rare earth surface-treated nanometer CaCO
3The filled polyimide matrix material is to obtain than higher interface binding power the hardness of raising polyimide resin matrix, and then the mechanical property and the abrasion resistance properties of raising matrix material.
Background technology
Polyimide is the organic polymer that contains imide group on the class main chain, owing to have very stable fragrant heterocycle structure unit in the molecule, makes it have the incomparable excellent properties of other superpolymer.Polyimide thermotolerance and radioresistance are good, and stable under high temperature, high vacuum and irradiation, the performance thing is few, can be in the medium-term and long-term use of 260 ℃ atmosphere, and the short-term use temperature can reach 460 ℃; The physical strength height, slow with the rising decline of temperature, more than 260 ℃, its tensile strength is also slower than aluminium with variation of temperature; Creep resisting ability is strong, under comparatively high temps, and its creep rate even also littler than aluminium; When under metal to-metal contact, rubbing, can play self-lubricating function, and static friction coefficient and kinetic friction coefficient are very approaching, prevent that the ability of creeping is good to the face that rubs is shifted with metal pair.Polyimide is the very potential body material that is applied to tribological field of a class, but pure polyimide is because of lower tension, ultimate compression strength, be not suitable for using as friction materials separately, so, adding various fillers and make the composite polyimide material member in matrix, is one of its principal mode of using in tribological field.Polyimide is applied to as self-lubricating abrasion-proof material in the friction system in fields such as space flight, is subjected to the very big attention of national defense and military and sophisticated technology department day by day.
Nanometer CaCO
3Particle belongs to the enhancement type nanometer material, has enhancement for resin matrix.This nanoparticle does not generally have so-called quantum effect and quantum tunneling effect, but the surface effects that it has impels it to have high surface, very strong surface energy and Surface binding energy are arranged, when being used for the resin matrix enhancing, can obtain tangible reinforced effects.As nanometer CaCO
3Be dispersed in the organic matrix,, when playing enhancement, can not reduce the toughness of matrix material again because of dispersion size is little.Nanometer CaCO
3Plastics have the excellent properties that general matrix material does not have, and are a kind of brand-new hi tech and new materials, have good commercial development and application prospect.Nanometer CaCO
3For the enhancing modified of polyimide provides a brand-brand-new way, there is not correlation technique openly to report at present as yet.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of nanometer CaCO is provided
3/ composite polyimide material preparation method, it is simple to have technology, and the characteristics of low-cost high-efficiency can well be improved nanometer CaCO
3With the interface binding power of polyimide matrix, thus the over-all properties of raising matrix material.
For realizing such purpose, in the technical scheme of the present invention, at room temperature adopt rare-earth modifier to nanometer CaCO earlier
3Carry out surface modification treatment, the nanometer CaCO after will handling again
3Put into the ball mill ball milling, then with the nanometer CaCO behind the ball milling
3Mechanical blending is carried out with the polyimide powder in the oven dry back, control nanometer CaCO
3Weight percent be 0.8～8% of mixed powder, again mixed powder is put into mould compression moulding, obtain rare earth modified nano CaCO through high temperature sintering
3/ composite polyimide material is made nanometer CaCO by mechanical workout again
3/ composite polyimide material sample or part.Wherein, the component of rare-earth modifier comprises rare earth compound, ethanol, ethylenediamine tetraacetic acid (EDTA), ammonium chloride, nitric acid and urea.
Composite material and preparation method thereof of the present invention is specific as follows:
1, with nanometer CaCO
3Immerse in the rare-earth modifier and soaked 2～4 hours, filter the back oven dry; The weight percentages of components of described rare-earth modifier is: rare earth compound 0.5～2.5%, ethanol 93.5～98.85%, ethylenediamine tetraacetic acid (EDTA) 0.1～0.8%, ammonium chloride 0.3～1%, nitric acid 0.05～0.7%, urea 0.2～1.5%.
2, the nanometer CaCO after will handling
3Mix with distilled water, be made into nanometer CaCO
3Weight percent be 3～12% solution, put into planetary ball mill ball milling 20～70min, rotating speed is 150～560r/min, with the nanometer CaCO behind the ball milling
3After putting into the abundant oven dry of baking oven, carry out mechanical blending, control nanometer CaCO with the polyimide powder
3Weight percent be 0.8～8% of mixed powder.
3, mixed powder is put into mould, furnace temperature is warming up to 250～260 ℃, keep 60～65min, obtain the premolding blank.
4, the premolding blank is carried out preformed, pressure-controlling is at 10.5～14.5MPa, is warming up to 320～360 ℃ with 60 ℃/hour speed again, is incubated 1 hour, makes the molding compound moulding.
5, adopt subsequently with the stove temperature reduction way and cool to 200 ℃, pressure remains constant in whole temperature-fall period; After temperature drops to below 200 ℃, pressure is removed, the matrix material after the compression molding is taken out cooling together with mould, make nanometer CaCO
3/ composite polyimide material.
The nanometer CaCO that the present invention makes
3/ composite polyimide material can pass through mechanical workout again, makes nanometer CaCO
3/ composite polyimide material sample or part.
Rare earth compound described in the present invention can be Lanthanum trichloride, Cerium II Chloride, lanthanum trioxide or cerium oxide.
The present invention is applicable to nanometer CaCO
3Strengthen composite polyimide material, wherein polyimide comprises the thermoplastic polyimide of the various trades mark, as GCPI
TMDeng.
The present invention adopts rare-earth modifier, ball mill to handle nanometer CaCO
3, can improve the interface binding power of matrix material better, improve nanometer CaCO
3Dispersiveness, thereby improve the tribological property and the mechanical property of matrix material more significantly, and the rare-earth modifier for treatment processing method is simple, cost is low, environmentally safe is handled back nanometer CaCO
3Can not bond together good manufacturability.Adopt the matrix material of the inventive method preparation, wear resistance is good, and especially the anti impact wear-proof ability significantly improves, and its tensile strength, flexural strength and impelling strength are significantly improved.
Embodiment
Below by specific embodiment technical scheme of the present invention is further described, but do not constitute limitation of the invention.
Embodiment 1
Used starting material comprise: the GCPI that polyimide resin powder, Changzhou extensively become plastics company limited to produce
TMType, 150 orders.Nanometer CaCO
3: Inner Mongol Meng Xi nano material limited-liability company, median size is 50～70nm.
1, earlier to nanometer CaCO
3Carry out pre-treatment, with nanometer CaCO
3At room temperature immerse in the rare-earth modifier, soaked 2.5 hours, filter the back oven dry.Each weight percentages of components is as follows in the rare-earth modifier: Lanthanum trichloride 0.5%, ethanol 97.02%, ethylenediamine tetraacetic acid (EDTA) 0.5%, ammonium chloride 0.7%, nitric acid 0.48%, urea 0.8%.
2, the nanometer CaCO that processing is obtained
3Mix with distilled water, be made into nanometer CaCO
3Weight percent be 3% solution, put into planetary ball mill ball milling 35min, rotating speed is 150r/min.With the nanometer CaCO that obtains behind the ball milling
3The baking oven of putting into 110 ℃ is fully dried, and carries out the powerful stirring of machinery after mixing with the polyimide powder.In the mixed powder: the weight percent of nanometer CaCO3 is 1.6%, and the weight percent of polyimide is 98.4%.
3, the mixed powder after will stirring is put into plate vulcanization machine die for molding, earlier furnace temperature is warming up to about 260 ℃, keeps 65 minutes, obtains the premolding blank.
4, the premolding blank is carried out preformed, this moment pressure-controlling about 11MPa, and then be warming up to about 320 ℃ with 60 ℃/hour speed, be incubated 1 hour, make the molding compound moulding.
5, lower the temperature subsequently, adopt with the stove temperature reduction way, cool to 200 ℃, concrete temperature fall time is decided on envrionment conditions.Pressure remains at 11MPa in whole temperature-fall period.After temperature drops to below 200 ℃, pressure is removed, the matrix material after the compression molding is taken out together with mould,, obtain rare earth modified nano CaCO with the room temperature cooling
3/ composite polyimide material.
The nanometer CaCO that makes according to the method described above
3/ composite polyimide material, recording its tensile strength according to standard is 78MPa; Routine in contrast, at identical nanometer CaCO
3Under content and the composite material preparation process condition, without the nanometer CaCO of rare earth modified processing
3Strengthening the composite polyimide material tensile strength is 63MPa.As can be seen, rare-earth modifier for treatment can obviously improve the tensile property of matrix material.
Above-mentioned matrix material machinery is processed into sample, carries out on the MPV200 type that the is determined at friction wear testing machine of friction coefficient of composite material and abrasion loss, before each test, sample and antithesis ring surface acetone cotton balls scrub.Test-results: frictional coefficient is less than 0.18, and load is when 480N, and abrasion loss is 230m/mg; Nanometer CaCO without rare earth modified processing
3The frictional coefficient that strengthens composite polyimide material is: 0.24, and load is when 480N, and abrasion loss is 263m/mg;
Embodiment 2
Used starting material are: the GCPI that polyimide resin powder, Changzhou extensively become plastics company limited to produce
TMType, 150 orders.Nanometer CaCO
3: Inner Mongol Meng Xi nano material limited-liability company, median size is 50～70nm.
1, earlier to nanometer CaCO
3Carry out pre-treatment, with nanometer CaCO
3At room temperature immerse in the rare-earth modifier, soaked 3 hours, filter the back oven dry.Each weight percentages of components is as follows in the rare-earth modifier: Cerium II Chloride 0.7%, ethanol 97%, ethylenediamine tetraacetic acid (EDTA) 0.3%, ammonium chloride 0.5%, nitric acid 0.5%, urea 1%.
2, the nanometer CaCO that processing is obtained
3Mix with distilled water, be made into nanometer CaCO
3Weight percent be 8% solution, put into planetary ball mill ball milling 50min, rotating speed is 200r/min.With the nanometer CaCO that obtains behind the ball milling
3The baking oven of putting into 110 ℃ is fully dried, and carries out the powerful stirring of machinery after mixing with the polyimide powder.In the mixed powder: the weight percent of nanometer CaCO3 is 3.8%, and the weight percent of polyimide is 96.2%.
3, the mixed powder after will stirring is put into plate vulcanization machine die for molding, earlier furnace temperature is warming up to about 260 ℃, keeps 60 minutes, obtains the premolding blank.
4, the premolding blank is carried out preformed, this moment pressure-controlling about 12MPa, and then be warming up to about 330 ℃ with 60 ℃/hour speed, be incubated 1 hour, make the molding compound moulding.
5, lower the temperature subsequently, adopt, cool to 200 ℃ with the stove temperature reduction way.Pressure remains at 12MPa in whole temperature-fall period.After temperature drops to below 200 ℃, pressure is removed, the matrix material after the compression molding is taken out together with mould,, obtain rare earth modified nano CaCO with the room temperature cooling
3/ composite polyimide material.
Above-mentioned materials is machined into shock test sample and rub(bing)test sample.Utilize MMD-10 type metope wear testing machine, matrix material is carried out the friction and wear behavior test, and with the nanometer CaCO that handles without rare earth
3The filled polyimide matrix material compares, and experimental result shows: the nanometer CaCO that the present invention handles through rare earth
3The friction and wear behavior of/composite polyimide material is better than the nanometer CaCO without the rare earth processing
3/ composite polyimide material.
Embodiment 3
Used starting material are: the GCPI that polyimide resin powder, Changzhou extensively become plastics company limited to produce
TMType, 150 orders.Nanometer CaCO
3: Inner Mongol Meng Xi nano material limited-liability company, median size is 50～70nm.
1, earlier to nanometer CaCO
3Carry out pre-treatment, with nanometer CaCO
3At room temperature immerse in the rare-earth modifier, soaked 4 hours, filter the back oven dry.Each weight percentages of components is as follows in the rare-earth modifier: cerium oxide 1.2%, alcohol 95 .4%, ethylenediamine tetraacetic acid (EDTA) 0.6%, ammonium chloride 0.8%, nitric acid 0.7%, urea 1.3%.
2, the nanometer CaCO3 that processing is obtained mixes with distilled water, and the weight percent that is made into nanometer CaCO3 is 12% solution, puts into planetary ball mill ball milling 60min, and rotating speed is 450r/min.With the nanometer CaCO that obtains behind the ball milling
3The baking oven of putting into 110 ℃ is fully dried, and carries out the powerful stirring of machinery after mixing with the polyimide powder.In the mixed powder: the weight percent of nanometer CaCO3 is 8%, and the weight percent of polyimide is 92%.
3, the mixed powder after will stirring is put into plate vulcanization machine die for molding, earlier furnace temperature is warming up to about 250 ℃, keeps 65 minutes, obtains the premolding blank.
4, the premolding blank is carried out preformed, this moment pressure-controlling about 14MPa, and then be warming up to about 360 ℃ with 60 ℃/hour speed, be incubated 1 hour, make the molding compound moulding.
5, lower the temperature subsequently, adopt, cool to 200 ℃ with the stove temperature reduction way.Pressure remains at 14MPa in whole temperature-fall period.After temperature drops to below 200 ℃, pressure is removed, the matrix material after the compression molding is taken out together with mould,, obtain rare earth modified nano CaCO with the room temperature cooling
3/ composite polyimide material.
The nanometer CaCO that makes according to the method described above
3/ composite polyimide material, recording its tensile strength according to standard is 68MPa.
Above-mentioned matrix material machinery is processed into sample, carries out on the MPV200 type that the is determined at friction wear testing machine of friction coefficient of composite material and abrasion loss, before each test, sample and antithesis ring surface acetone cotton balls scrub.Test-results: frictional coefficient is 0.19, and load is when 480N, and abrasion loss is 240m/mg.
Claims (3)
1, a kind of nanometer CaCO
3/ composite polyimide material preparation method is characterized in that comprising the steps:
1) with nanometer CaCO
3Immerse in the rare-earth modifier and soaked 2～4 hours, filter the back oven dry; The weight percentages of components of described rare-earth modifier is: rare earth compound 0.5～2.5%, ethanol 93.5～98.85%, ethylenediamine tetraacetic acid (EDTA) 0.1～0.8%, ammonium chloride 0.3～1%, nitric acid 0.05～0.7%, urea 0.2～1.5%;
2) the nanometer CaCO after will handling
3Mix with distilled water, be made into nanometer CaCO
3Weight percent be 3～12% solution, put into planetary ball mill ball milling 20～70min, rotating speed is 150～560r/min, with the nanometer CaC0 behind the ball milling
3After putting into the abundant oven dry of baking oven, carry out mechanical blending, control nanometer CaCO with the polyimide powder
3Weight percent be 0.8～8% of mixed powder;
3) mixed powder is put into mould, furnace temperature is warming up to 250～260 ℃, keep 60～65min, obtain the premolding blank;
4) the premolding blank is carried out preformed, pressure-controlling is at 10.5～14.5MPa, is warming up to 320～360 ℃ with 60 ℃/hour speed again, is incubated 1 hour, makes the molding compound moulding;
5) adopt subsequently with the stove temperature reduction way and cool to 200 ℃, pressure remains constant in whole temperature-fall period; After temperature drops to below 200 ℃, pressure is removed, the matrix material after the compression molding is taken out cooling together with mould, make nanometer CaCO
3/ composite polyimide material.
2, according to the nanometer CaCO of claim 1
3/ composite polyimide material preparation method is characterized in that described rare earth compound is Lanthanum trichloride, Cerium II Chloride, lanthanum trioxide or cerium oxide.
3, according to the nanometer CaCO of claim 1
3/ composite polyimide material preparation method is characterized in that described polyimide is a thermoplastic polyimide.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910055616A CN101629016A (en) | 2009-07-30 | 2009-07-30 | Preparation method of nano CaCO3/polyimide composite |
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| CN200910055616A CN101629016A (en) | 2009-07-30 | 2009-07-30 | Preparation method of nano CaCO3/polyimide composite |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106280560A (en) * | 2016-08-05 | 2017-01-04 | 中玺新材料（安徽）有限公司 | A kind of anti-scratch composite calcium carbonate and preparation method thereof |
| CN106496636A (en) * | 2016-10-24 | 2017-03-15 | 天津城建大学 | A kind of waste stone dust surface modifying method based on wet grinding |
| CN107033520A (en) * | 2016-10-21 | 2017-08-11 | 广西师范学院 | The preparation method of wear-resisting SBS material for sole of shoe |
-
2009
- 2009-07-30 CN CN200910055616A patent/CN101629016A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106280560A (en) * | 2016-08-05 | 2017-01-04 | 中玺新材料（安徽）有限公司 | A kind of anti-scratch composite calcium carbonate and preparation method thereof |
| CN107033520A (en) * | 2016-10-21 | 2017-08-11 | 广西师范学院 | The preparation method of wear-resisting SBS material for sole of shoe |
| CN106496636A (en) * | 2016-10-24 | 2017-03-15 | 天津城建大学 | A kind of waste stone dust surface modifying method based on wet grinding |
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Open date: 20100120 |