CN102219994B - Heat conducting nanometer material and preparation method and application thereof - Google Patents
Heat conducting nanometer material and preparation method and application thereof Download PDFInfo
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- CN102219994B CN102219994B CN 201110134843 CN201110134843A CN102219994B CN 102219994 B CN102219994 B CN 102219994B CN 201110134843 CN201110134843 CN 201110134843 CN 201110134843 A CN201110134843 A CN 201110134843A CN 102219994 B CN102219994 B CN 102219994B
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Abstract
The invention discloses a heat conducting nanometer material and a preparation method and application thereof. The composite material comprises the following raw materials in percentage by mass: 51.5 to 91 percent of polyamide 66, 1 to 1.5 percent of silicone resin, 2 to 8 percent of thermotropic liquid crystal Vectra A 950, 5 to 40 percent of nanometer scale halloysite powder and 1 to 7 percent of ethylene-propylene non-conjugated diene elastomer grafting maleic anhydride. The preparation method comprises the following steps of: drying natural halloysite by using hot air, and crushing; preparing mixed solution from the crushed halloysite powder, distilled water and powdery sodium hexametaphosphate, and standing for demixing; and drying the clarified solution by using the hot air, crushing and sieving to obtain purified nanometer scale halloysite powder. The halloysite powder is subjected to nanocrystallization, and a proper amount of compatilizer is added to improve compatibility between the halloysite and a matrix, so that the composite material has higher performance compared with that achieved by the conventional mixed composite technology, and the tensile strength, flexural strength and flexural modulus of the composite material are improved obviously.
Description
Technical field
The present invention relates to a kind of thermally conductive material, particularly relate to the heat conducting nano material that contains halloysite nanotubes and polyamide 66, this material is an IN-SITU HYBRID COMPOSITES.
Background technology
Polymeric amide excellent comprehensive performance makes it in the range of application in fields such as electronics, electrical equipment more and more widely.Along with the developing rapidly of hyundai electronics package technique, packing density improve rapidly; The a large amount of heats that require components and parts to produce in the course of the work must be able in time distribute and conduct; Otherwise will have influence on the normality of system works and the stability of component size, thereby the heat conductivility of material is had higher requirement.But because the heat conductivility of plastic material is generally bad, even best its thermal conductivity of high density polyethylene(HDPE) of thermal conductivity also is merely 0.44W/ (m.K), the heat conductivility that therefore improves polyamide compoiste material has practical meaning.
The material of excellent thermal conductivity must possess two conditions: the formation and the direction of heat flow of heat conduction network chain are consistent with the orientation of heat conduction network chain in the matrix.The main method that the preparation heat-conducting plastic is gone up in industry at present is in polymeric matrix, to fill high heat conduction component to prepare polymer-based composite heat conducting material.Through contact between the high-load filler and interaction, in system, form similar chain and netted distributional pattern---heat conduction network chain, thereby improve the thermal conductivity of matrix material.Mineral filler commonly used is graphite, pottery, thomel, carbon black, Al
2O
3, MgO, AlN, BN etc.But, in heat conduction, have insulativity in order to make polymer composite, often do not add graphite, carbon black, etc. the high filler of specific conductivity; Thereby factor is not suitable for industrial production and makes low-cost, high performance moulded heat-conductive insulated plastics and AlN, BN are respectively because its cost is more higher, processing characteristics is bad etc.; The more important thing is that the adding of a large amount of mineral fillers how when improving the matrix material thermal conductivity, keeps other excellent properties of matrix resin to become the important directions of heat conductive insulating matrix material research as far as possible.
(Xiao Bo, Liu Shumei, Chen Jun such as Xiao Bo; The structure of PA66/TLCP/ halloysite nanotubes trielement composite material and performance [J]. engineering plastics are used, 37 (4), 10～14) liquid crystal and halloysite nanotubes and polyamide 66 is compound; Improved the mechanical property of matrix material, but the halloysite nanotubes in this technology is prone to reunion, halloysite content is merely 5wt%; Make that the raising of composite materials property is limited, and the prepared composite material do not possess heat conductivility; On the other hand, the liquid crystal content of 10wt% is not from reach the purpose that reduces production costs at all.
The content of invention
The heat conductivility that the objective of the invention is to plastic material is generally bad, and a kind of Performances of Novel Nano-Porous meter level mineral filler that can improve polymeric matrix mechanical property and heat conductivility simultaneously and preparation method thereof is provided.
Halloysite (HNTs) mainly is made up of silicon-oxy tetrahedron and alumina octahedral as natural silicate minerals.Can know Al in the halloysite through the XRD test
2O
3Content up to 40.414%, and Al
2O
3Be highly heat-conductive material, help to promote the heat conductivility of matrix material in theory; On the other hand, HNTs and matrix have consistency preferably, and it self can disperse in system when promoting TLCP to become fibre preferably, so the adding of high-content HNTs is expected to reach simultaneously the purpose that improves composite materials property and heat conductivility; Moreover HNTs nanotube and TLCP formed fento in matrix helps promoting that the orientation of heat conduction network chain is consistent with direction of heat flow, thereby intensifying heat transfer improves the thermal conductivity of material effectively.The present invention will and be used for nylon through preparation nano grade inorganic filler and thermotropic liquid crystal; Prepare the IN-SITU HYBRID COMPOSITES that has the heat conductivility and the mechanical property of excellence concurrently; Not only enriched the modified method of polymeric amide; And reduce cost, quickened the industrialized paces of original position compounding technology greatly, effectively solve the liquid crystal fancy price, the industrialized problem of difficult realization.
The object of the invention is realized through following technical scheme:
A kind of heat conducting nano composite material, by percentage to the quality, the raw material of this matrix material consists of:
Said nano level halloysite powder prepares through following method: contained brown in the natural halloysite is partly removed, pulverized after 10～15 hours 80 ℃～100 ℃ following warm air dryings; Halloysite powder, zero(ppm) water and the powdery Sodium hexametaphosphate 99 got after the pulverizing are mixed with mixed solution with mass ratio 1: 10: 0.002～0.01; Stir at normal temperatures after 22～28 hours and left standstill again 70～76 hours; The settled solution of getting behind the standing demix becomes block 80 ℃～100 ℃ following warm air dryings 18～24 hours to halloysite; Block halloysite is pulverized, and crossed 100～200 mesh sieves, obtain nano level pure halloysite powder.
The preparation method of said heat conducting nano composite material comprises the steps and processing condition:
(1) preparation of nano level halloysite powder
Contained brown in the natural halloysite is partly removed, pulverized after 10～15 hours 80 ℃～100 ℃ following warm air dryings; Halloysite powder, zero(ppm) water and the powdery Sodium hexametaphosphate 99 got after the pulverizing are mixed with mixed solution with mass ratio 1: 10: 0.002～0.01; Stir at normal temperatures after 22～28 hours and left standstill again 70～76 hours; The settled solution of getting behind the standing demix becomes block 80 ℃～100 ℃ following warm air dryings 18～24 hours to halloysite; Block halloysite is pulverized, and crossed 100～200 mesh sieves, obtain nano level pure halloysite powder;
(2) preparation of heat conducting nano composite material: after the material vacuum drying with matrix material, mix, extrude, granulation, injection moulding, make heat conducting nano composite material.
For further realizing the object of the invention, the material vacuum drying of described matrix material is meant that polyamide 66 and thermotropic liquid crystal Vectra A 950 (TLCP) raw material were 100 ℃～110 ℃ following vacuum-dryings 10～12 hours; Nano level halloysite powder was 90 ℃～100 ℃ following vacuum-dryings 8～10 hours; Ethylene-propylene non-conjugated diene elastomerics grafted maleic anhydride (EPDM-g-MAH) and silicone resin (GM100) are all 70 ℃～80 ℃ following vacuum-dryings 8～10 hours.
Extruder barrel mouth temperature is that 250 ℃～260 ℃, transportation section temperature are that 260 ℃～270 ℃, compression section temperature are that 270 ℃～290 ℃, metering zone temperature are 290 ℃～280 ℃; Nozzle temperature is 275 ℃～280 ℃; Screw speed is 180～200r/min; Rate of feeding is 15～20r/min.
With institute's granulation in vacuum drying oven behind 100 ℃～110 ℃ down dry 10～12h and under sealing condition, be cooled to room temperature.
The used injecting machine material tube mouth temperature of injection moulding is that 250 ℃～260 ℃, transportation section temperature are that 260 ℃～270 ℃, compression section temperature are that 270 ℃～290 ℃, metering zone temperature are 290 ℃～295 ℃; Nozzle temperature is 295 ℃～300 ℃; Die temperature is 80 ℃～100 ℃; Screw speed is 100～120r/min; The injection back pressure is 60～80Mpa.
Mix compounding technology with respect to existing, the present invention has following advantage and beneficial effect:
(1) the present invention is the halloysite powder nanometerization, and prevents the halloysite powder agglomeration in the method for extruding preceding employing " the vacuum blend is dry ", to promote the formation of nano effect; Be aided with an amount of compatilizer and improve the consistency between halloysite and the matrix, make matrix material have more excellent performance with respect to the existing compounding technology that mixes.Be all the sample contrast of 20wt% with halloysite content: its tensile strength, flexural strength and modulus in flexure have improved 15.6%, 65.9%, 66.7% respectively; Heat-drawn wire has improved 16 ℃.
(2) the present invention is through the adding of lubricant; Halloysite content is increased to 40%; Mechanical property and the heat conductivility of realizing matrix material first are improved simultaneously; The matrix material thermal conductivity is increased to 0.45W/ (m.K), is superior to the best macromolecular material high density polyethylene(HDPE) 0.44W/ (m.K) of heat conductivility.
(3) the present invention is through improving the content of halloysite, reduced cost greatly, broken the liquid crystal high price limitation, quickened the industrialized paces of original position compounding technology, for the dimensional stability of improving nylon products new research direction is provided simultaneously.
Description of drawings
Fig. 1 is the tensile strength and the flexural strength curve of the matrix material of different content HNTs among the embodiment 2.
Fig. 2 is the tensile modulus and the modulus in flexure curve of the matrix material of different content HNTs among the embodiment 2.
Fig. 3 is the impact strength curve of the matrix material of different EPDM-g-MAH content among the embodiment 4,5.
Fig. 4 is the tensile strength curve of the matrix material of different HNTs content among the embodiment 6,7,8.
Fig. 5 is the flexural strength and the modulus in flexure curve of the matrix material of different HNTs content among the embodiment 6,7,8.
Fig. 6 is the heat-drawn wire curve of the matrix material of different HNTs content among the embodiment 6,7,8.
Fig. 7 is the thermal conductivity curve of the matrix material of different HNTs content among the embodiment 6,7,8.
Fig. 8 is the storage modulus curve of the matrix material of different HNTs content among the embodiment 6,7,8.
Fig. 9 is the face SEM photo absolutely of quenching of the matrix material during 4wt% liquid crystal content among the embodiment 6.
Figure 10 is the face SEM photo absolutely of quenching of the matrix material of 30wt%HNTs content among the embodiment 8.
Concrete embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is described further, but embodiments of the invention are not limited to this.
Contained brown in the natural halloysite is partly removed, pulverized after 10 hours 90 ℃ of following warm air dryings; Halloysite powder, zero(ppm) water and the powdery Sodium hexametaphosphate 99 got after the pulverizing are mixed with solution with mass ratio at 1: 10: 0.002; Stir at normal temperatures after 24 hours and left standstill again 72 hours; The settled solution of getting behind the standing demix becomes block 90 ℃ of following warm air dryings 24 hours to halloysite; Block halloysite is pulverized, and crossed 200 mesh sieves, obtain nano level pure halloysite powder; Nano level halloysite powder has tubular structure, can be referred to as halloysite nanotubes (HNTs), and HNTs is rich in high heat conduction component aluminium sesquioxide (Al
2O
3), the aluminium sesquioxide mass content is up to 40.4%.
With polyamide 66 and Vectra A 950 (TLCP) raw material 110 ℃ of following vacuum-dryings 10 hours; The above-mentioned halloysite nanotubes that makes (HNTs) was 100 ℃ of following vacuum-dryings 8 hours; Dried raw material is prepared blend by following quality than proportioning: PA66: TLCP: HNTS was respectively 93.5: 4: 2.5; 91: 4: 5; 86: 4: 10; 81: 4: 15; The blend gross weight is 550 grams, again 100 ℃ of following vacuum-dryings 4 hours, and in closed container, is cooled to room temperature after mixing.
After mixing by proportioning, the raw material of matrix material,, prevents that the halloysite powder from reuniting when blanking with hydroxyl and the polyamide 66 interaction that promotes the halloysite surface again 90 ℃～100 ℃ following vacuum-dryings 4～5 hours.For preventing the halloysite suction, the raw material of described matrix material must be cooled to room temperature under vacuum condition, uses as extruding sample.
With ready blend extrude, granulation: extruder barrel mouth temperature is that 250 ℃, transportation section temperature are that 260 ℃, compression section temperature are that 280 ℃, metering zone temperature are 290 ℃; Nozzle temperature is 280 ℃; Screw speed is 200r/min; Rate of feeding is 20r/min; Extrude silk pelletizing after water-cooled.
With institute's granulation (silk after extruding through forcing machine is granulation through the dicing machine pelletizing) in injection moulding behind the dry 10h in vacuum drying oven under 100 ℃: injecting machine material tube mouth temperature is that 250 ℃～260 ℃, transportation section temperature are that 260 ℃～270 ℃, compression section temperature are that 270 ℃～290 ℃, metering zone temperature are 290 ℃～295 ℃; Nozzle temperature is 295 ℃～300 ℃; Screw speed is 100r/min; The injection back pressure is 80Mpa; 80 ℃ of mould temperature.Dwell time is 8s, obtains the standard testing batten after the demoulding.
Contained brown in the natural halloysite is partly removed, pulverized after 10 hours 90 ℃ of following warm air dryings; Halloysite powder, zero(ppm) water and the powdery Sodium hexametaphosphate 99 got after the pulverizing are mixed with solution with mass ratio at 1: 10: 0.5%; Stir at normal temperatures after 24 hours and left standstill again 72 hours; The settled solution of getting behind the standing demix becomes block 90 ℃ of following warm air dryings 24 hours to halloysite; Block halloysite is pulverized, and crossed 200 mesh sieves, obtain nano level pure halloysite powder;
With polyamide 66 and Vectra A 950 raw materials 110 ℃ of following vacuum-dryings 10 hours; Homemade halloysite nanotubes (HNTs) was 100 ℃ of following vacuum-dryings 8 hours; Dried raw material was respectively 93.5: 4: 2.5 by following proportioning (mass ratio) preparation blend: PA66/TLCP/HNTS; 91: 4: 5; 86: 4: 10; 81: 4: 15; The blend gross weight is 550 grams, again 100 ℃ of following vacuum-dryings 4 hours, and in closed container, is cooled to room temperature after mixing.
With ready blend extrude, granulation: extruder barrel mouth temperature is that 250 ℃, transportation section temperature are that 260 ℃, compression section temperature are that 280 ℃, metering zone temperature are 290 ℃; Nozzle temperature is 280 ℃; Screw speed is 200r/min; Rate of feeding is 20r/min; Extrude silk pelletizing after water-cooled.
With institute's granulation in injection moulding behind the dry 10h in vacuum drying oven under 100 ℃: injecting machine material tube mouth temperature is that 250 ℃～260 ℃, transportation section temperature are that 260 ℃～270 ℃, compression section temperature are that 270 ℃～290 ℃, metering zone temperature are 290 ℃～295 ℃; Nozzle temperature is 295 ℃～300 ℃; Screw speed is 100r/min; The injection back pressure is 80Mpa; 80 ℃ of mould temperature.Dwell time is 8s, obtains the standard testing batten after the demoulding.
Embodiment 3
Contained brown in the natural halloysite is partly removed, pulverized after 10 hours 90 ℃ of following warm air dryings; Halloysite powder, zero(ppm) water and the powdery Sodium hexametaphosphate 99 got after the pulverizing are mixed with solution with mass ratio at 1: 10: 1.0%; Stir at normal temperatures after 24 hours and left standstill again 72 hours; The settled solution of getting behind the standing demix becomes block 90 ℃ of following warm air dryings 24 hours to halloysite; Block halloysite is pulverized, and crossed 200 mesh sieves, obtain nano level pure halloysite powder;
With polyamide 66 and Vectra A 950 raw materials 110 ℃ of following vacuum-dryings 10 hours; Homemade halloysite nanotubes (HNTs) was 100 ℃ of following vacuum-dryings 8 hours; Dried raw material is prepared blend by following proportioning (mass ratio): PA66/TLCP/H NTS was respectively 93.5: 4: 2.5; 91: 4: 5; 86: 4: 10; 81: 4: 15; The blend gross weight is 550 grams, again 100 ℃ of following vacuum-dryings 4 hours, and in closed container, is cooled to room temperature after mixing.
With ready blend extrude, granulation: extruder barrel mouth temperature is that 250 ℃, transportation section temperature are that 260 ℃, compression section temperature are that 280 ℃, metering zone temperature are 290 ℃; Nozzle temperature is 280 ℃; Screw speed is 200r/min; Rate of feeding is 20r/min; Extrude silk pelletizing after water-cooled.
With institute's granulation in injection moulding behind the dry 10h in vacuum drying oven under 100 ℃: injecting machine material tube mouth temperature is that 250 ℃～260 ℃, transportation section temperature are that 260 ℃～270 ℃, compression section temperature are that 270 ℃～290 ℃, metering zone temperature are 290 ℃～295 ℃; Nozzle temperature is 295 ℃～300 ℃; Screw speed is 100r/min; The injection back pressure is 80Mpa; 80 ℃ of mould temperature.Dwell time is 8s, obtains the standard testing batten after the demoulding.
Embodiment 4
Adopt the preparation method of halloysite among the embodiment 2, purify, pulverize halloysite subsequent use.
With polyamide 66 and Vectra A 950 (TLCP) raw material 110 ℃ of following vacuum-dryings 10 hours; Homemade halloysite nanotubes (HNTs) was 100 ℃ of following vacuum-dryings 8 hours; Ethylene-propylene non-conjugated diene elastomerics grafted maleic anhydride (EPDM-g-MAH) was 70 ℃ of following vacuum-dryings 8 hours; Dried raw material was respectively 80: 4: 15 by following proportioning (mass ratio) preparation blend: PA66/TLCP/HNTS/EPDM-g-MAH: 1; 78: 4: 15: 3; The blend gross weight is 550 grams, again 100 ℃ of following vacuum-dryings 4 hours, and in closed container, is cooled to room temperature after mixing.
With ready blend extrude, granulation: extruder barrel mouth temperature is that 250 ℃, transportation section temperature are that 260 ℃, compression section temperature are that 280 ℃, metering zone temperature are 290 ℃; Nozzle temperature is 280 ℃; Screw speed is 200r/min; Rate of feeding is 20r/min; Extrude silk pelletizing after water-cooled.
With institute's granulation in injection moulding behind the dry 10h in vacuum drying oven under 100 ℃: injecting machine material tube mouth temperature is that 250 ℃～260 ℃, transportation section temperature are that 260 ℃～270 ℃, compression section temperature are that 270 ℃～290 ℃, metering zone temperature are 290 ℃～295 ℃; Nozzle temperature is 295 ℃～300 ℃; Screw speed is 100r/min; The injection back pressure is 80Mpa; 80 ℃ of mould temperature.Dwell time is 8s, obtains the standard testing batten after the demoulding.
Adopt the preparation method of halloysite among the embodiment 2, purify, pulverize halloysite subsequent use.
With polyamide 66 and Vectra A 950 (TLCP) raw material 110 ℃ of following vacuum-dryings 10 hours; Homemade halloysite nanotubes (HNTs) was 100 ℃ of following vacuum-dryings 8 hours; Ethylene-propylene non-conjugated diene elastomerics grafted maleic anhydride (EPDM-g-MAH) was 70 ℃ of following vacuum-dryings 8 hours; Dried raw material was respectively 76: 4: 15 by following proportioning (mass ratio) preparation blend: PA66/TLCP/HNTS/EPDM-g-MAH: 5; 74: 4: 15: 7; The blend gross weight is 550 grams, again 100 ℃ of following vacuum-dryings 4 hours, and in closed container, is cooled to room temperature after mixing.
With ready blend extrude, granulation: extruder barrel mouth temperature is that 250 ℃, transportation section temperature are that 260 ℃, compression section temperature are that 280 ℃, metering zone temperature are 290 ℃; Nozzle temperature is 280 ℃; Screw speed is 200r/min; Rate of feeding is 20r/min; Extrude silk pelletizing after water-cooled.
With institute's granulation in injection moulding behind the dry 10h in vacuum drying oven under 100 ℃: injecting machine material tube mouth temperature is that 250 ℃～260 ℃, transportation section temperature are that 260 ℃～270 ℃, compression section temperature are that 270 ℃～290 ℃, metering zone temperature are 290 ℃～295 ℃; Nozzle temperature is 295 ℃～300 ℃; Screw speed is 100r/min; The injection back pressure is 80Mpa; 80 ℃ of mould temperature.Dwell time is 8s, obtains the standard testing batten after the demoulding.
Adopt the preparation method of halloysite among the embodiment 2, purify, pulverize halloysite subsequent use.
With polyamide 66 and Vectra A 950 (TLCP) raw material 110 ℃ of following vacuum-dryings 10 hours; Homemade halloysite nanotubes (HNTs) was 100 ℃ of following vacuum-dryings 8 hours; Ethylene-propylene non-conjugated diene elastomerics grafted maleic anhydride (EPDM-g-MAH) was 70 ℃ of following vacuum-dryings 8 hours; Dried raw material was respectively 100: 0: 0 by following proportioning (mass ratio) preparation blend: PA66/TLCP/EPDM-g-MAH/HNTS: 0; 83: 4: 3: 10; The blend gross weight is 550 grams, again 100 ℃ of following vacuum-dryings 4 hours, and in closed container, is cooled to room temperature after mixing.
With ready blend extrude, granulation: extruder barrel mouth temperature is that 250 ℃, transportation section temperature are that 260 ℃, compression section temperature are that 280 ℃, metering zone temperature are 290 ℃; Nozzle temperature is 280 ℃; Screw speed is 200r/min; Rate of feeding is 20r/min; Extrude silk pelletizing after water-cooled.
With institute's granulation in injection moulding behind the dry 10h in vacuum drying oven under 100 ℃: injecting machine material tube mouth temperature is that 250 ℃～260 ℃, transportation section temperature are that 260 ℃～270 ℃, compression section temperature are that 270 ℃～290 ℃, metering zone temperature are 290 ℃～295 ℃; Nozzle temperature is 295 ℃～300 ℃; Screw speed is 100r/min; The injection back pressure is 80Mpa; 80 ℃ of mould temperature.Dwell time is 8s, obtains the standard testing batten after the demoulding.
Embodiment 7
Adopt the preparation method of halloysite among the embodiment 2, purify, pulverize halloysite subsequent use.
With polyamide 66 and Vectra A 950 (TLCP) raw material 110 ℃ of following vacuum-dryings 10 hours; Homemade halloysite nanotubes (HNTs) was 100 ℃ of following vacuum-dryings 8 hours; Ethylene-propylene non-conjugated diene elastomerics grafted maleic anhydride (EPDM-g-MAH) was 70 ℃ of following vacuum-dryings 8 hours; Dried raw material was respectively 73: 4: 3 by following proportioning (mass ratio) preparation blend: PA66/TLCP/EPDM-g-MAH/HNTS: 20; 63: 4: 3: 30.The blend gross weight is 550 grams, again 100 ℃ of following vacuum-dryings 4 hours, and in closed container, is cooled to room temperature after mixing.
With ready blend extrude, granulation: extruder barrel mouth temperature is that 250 ℃, transportation section temperature are that 260 ℃, compression section temperature are that 280 ℃, metering zone temperature are 290 ℃; Nozzle temperature is 280 ℃; Screw speed is 200r/min; Rate of feeding is 20r/min; Extrude silk pelletizing after water-cooled.
With institute's granulation in injection moulding behind the dry 10h in vacuum drying oven under 100 ℃: injecting machine material tube mouth temperature is that 250 ℃～260 ℃, transportation section temperature are that 260 ℃～270 ℃, compression section temperature are that 270 ℃～290 ℃, metering zone temperature are 290 ℃～295 ℃; Nozzle temperature is 295 ℃～300 ℃; Screw speed is 100r/min; The injection back pressure is 80Mpa; 80 ℃ of mould temperature.Dwell time is 8s, obtains the standard testing batten after the demoulding.
Embodiment 8
Adopt the preparation method of halloysite among the embodiment 2, purify, pulverize halloysite subsequent use.
With PA66 and TLCP raw material 110 ℃ of following vacuum-dryings 10 hours; Homemade halloysite nanotubes (HNTs) was 100 ℃ of following vacuum-dryings 8 hours; Ethylene-propylene non-conjugated diene elastomerics grafted maleic anhydride (EPDM-g-MAH) and silicone resin (GM100) are all 70 ℃ of following vacuum-dryings 8 hours; Dried raw material was respectively 53: 4: 3 by following proportioning (mass ratio) preparation blend: PA66/TLCP/EPDM-g-MAH/HNTS/GM100: 40: 0; 51.5: 4: 3: 40: 1.5.The blend gross weight is 550 grams, again 100 ℃ of following vacuum-dryings 4 hours, and in closed container, is cooled to room temperature after mixing.
With ready blend extrude, granulation: extruder barrel mouth temperature is that 250 ℃, transportation section temperature are that 260 ℃, compression section temperature are that 280 ℃, metering zone temperature are 290 ℃; Nozzle temperature is 280 ℃; Screw speed is 200r/min; Rate of feeding is 20r/min; Extrude silk pelletizing after water-cooled.
With institute's granulation in injection moulding behind the dry 10h in vacuum drying oven under 100 ℃: injecting machine material tube mouth temperature is that 250 ℃～260 ℃, transportation section temperature are that 260 ℃～270 ℃, compression section temperature are that 270 ℃～290 ℃, metering zone temperature are 290 ℃～295 ℃; Nozzle temperature is 295 ℃～300 ℃; Screw speed is 100r/min; The injection back pressure is 80Mpa; Die temperature is 80 ℃.Dwell time is 8s, obtains the standard testing batten after the demoulding.
Testing method:
The impact property test is carried out according to GB/T 1843-1996, adopts the B5113.300 type radial-boom impact tester of German Zwick material-testing machine manufactured that blend is carried out the experiment of socle girder notch shock.
Tensile property test is carried out according to GB/T 1040-2006, on the ZwickZ010 type tensile testing machine of German Zwick/Roell company, carries out stretching experiment, and draw speed is 50mm/min.
Bending property test is carried out according to GB/T 9341-2000, carries out crooked experiment at the 5500-R type universal testing machine of American I nstron manufactured
Adopt German Netzsch 242C type dynamic mechanical analysis appearance to measure the dynamic properties (DMA) of sample.Select the three-point bending pattern, 30 ℃～150 ℃ of TRs, 3 ℃/min of heat-up rate, frequency 1Hz, specimen size is 64 * 12.6 * 4mm.
Adopt Italian Xi Site (CE Λ ST) HDT type analysis appearance to measure the heat-drawn wire of sample.Select three-point bending pattern, specimen size 80 * 10 * 4mm, span 64mm, stress in bending 1.80Mpa, 120 ℃/h of temperature rise rate during measurement.
Thermal conductivity adopts the laser heat conducting instrument test, and probe temperature is 30 ℃.The master batch of making forms diameter and uses standard as 12.7mm, thickness as the thermal conductivity test of 2mm after at first using injection moulding machine with blend, and is reflective for preventing, with liquid carbon black black dyed on the sample two sides before the test, and the calculation formula of thermal conductivity (λ) is:
λ＝ρC
pa
In the formula: ρ-sample rate; C
p-specific heat capacity; The a-thermal diffusivity;
With the disconnected batten of extruding of quenching in the liquid nitrogen, with LEO1530VP type sem observation section surface topography, acceleration voltage is 10KV after metal spraying is handled 60s.
Fig. 1 and Fig. 2 are the Mechanics Performance Testing curves of the matrix material of different content HNTs among the embodiment 2.Compare (Xiao Bo with the prior art of identical halloysite content; Liu Shumei; The structure and the performance of .PA66/TLCP/ halloysite nanotubes trielement composite materials such as Zhao Jianqing, engineering plastics are used, and 2009; 37 (4): 10～14), the tensile strength of heat-conductive composite material, flexural strength and modulus in flexure have promoted 6%, 39.8%, 15.8% respectively.
The impact property test curve of the matrix material of different content compatilizer among Fig. 3 embodiment 4,5.The adding of compatilizer makes the relative prior art of the impact property of heat-conductive composite material improve 52.6%.
Fig. 4, the 5th, the Mechanics Performance Testing curve of the matrix material of the HNTs of different content among the embodiment 6,7,8.Prior art (Xiao Bo with identical halloysite content; Liu Shumei; The structure and the performance of .PA66/TLCP/ halloysite nanotubes trielement composite materials such as Zhao Jianqing; Engineering plastics are used, and 2009,37 (4): 10～14) contrast: its tensile strength, flexural strength and modulus in flexure have improved 15.6%, 65.9%, 66.7% respectively.HNTs shows the reinforcing effect of excellence like this to the PA66 matrix, be on the one hand because its surperficial hydroxyl can and the carboxamido-group of PA66 between form hydrogen bond, strengthen interaction between the two; Be on the other hand because halloysite nanotubes can be in matrix uniform distribution, its characteristic than big L/D ratio makes its effect of in matrix, playing transmitted load, thereby increases the intensity and the modulus of matrix material.
Fig. 6 is the heat-drawn wire curve of the matrix material of the HNTs of different content among the embodiment 6,7,8.(Xiao Bo, Liu Shumei, the structure and the performance of .PA66/TLCP/ halloysite nanotubes trielement composite materials such as Zhao Jianqing when the content of HNTs is all 20wt%; Engineering plastics are used; 2009,37 (4): 10～14), the heat-drawn wire of heat-conductive composite material has improved 16 ℃.And the heat-drawn wire of matrix material is increased to 154 ℃ the most at last, has greatly optimized the resistance toheat of matrix material.The raising of matrix material heat-drawn wire on the one hand is because halloysite self contains a certain amount of hydroxyl, and the interaction between itself and the carboxamido-group has limited the motion of PA66 chain, and matrix material is being heated and pressure is done the time spent and is difficult for taking place deformation; On the other hand, halloysite has bigger length-to-diameter ratio as nano level tubular material, and piped HNTs can play the effect of transmitted load and stress bridge in the PA66 matrix, improves its heat-drawn wire in the time of the intensity of increase matrix material and modulus.
Fig. 7 is the thermal conductivity curve of the matrix material of the HNTs of different content among the embodiment 6,7,8.When the mass content of halloysite was 40%, the thermal conductivity of matrix material was superior to the best macromolecular material high density polyethylene(HDPE) 0.44W/ (m.K) of heat conductivility up to 0.445W/ (m.K).Be because of increase on the one hand along with halloysite content; Make contact and interactional chance between the halloysite increase; Formed and be similar to chain or netted structural form, thus the inner heat conduction network chain of constitution system, especially when adding nano level filler; Because surface-area is big, this trend is more obvious; On the other hand, the HNTs nanotube self can be orientated along the shearing force direction when TLCP forms fento in matrix promoting preferably, when the orientation of heat conduction network chain consistent with direction of heat flow, intensifying heat transfer more effectively.Dual function makes the thermal conductivity of matrix material be greatly improved.
Fig. 8 is the storage modulus curve of the matrix material of the HNTs of different content among the embodiment 6,7,8, has shown good synergistic between PA and the HNTs.
Fig. 9 is the face SEM photo absolutely of quenching of the matrix material of the HNTs of different content among the embodiment 6,7,8; Can see the formed diameter of TLCP clearly is the nano level fento about 100nm, and this is one of reason of heat-conductive composite material mechanical property and heat conductivility rising.
Can clearly see HNTs among Figure 10 at the inner heat conduction network that is constituted of matrix, this is the basic reason that thermal conductivity of composite materials sharply rises.HNTs can be in the PA66 matrix disperses preferably and occurs significantly reuniting, and mainly gives the credit to its structure and composition: HNTs piped geometrical dimension makes it compare general spheroidal particle to disperse more easily, be orientated; The hydroxyl of certain number is contained in the outside of HNTs, but far below the concentration that can promote that HNTs reunites, the form with secondary valence bonds such as hydrogen bond or Fan Dehuali between the structural unit combines, and double factor makes HNTs compare general nano material to disperse more easily.Thereby through simple contour machining procedure, HNTs just can disperse well in the PA66 matrix and have stronger interface to combine with it, and this also is the potential advantages that HNTs is had as a kind of novel enhanced material.
Claims (6)
1. a heat conducting nano composite material is characterized in that, by percentage to the quality, the raw material of this matrix material consists of:
Said nano level halloysite powder prepares through following method: contained brown in the natural halloysite is partly removed, pulverized after 10～15 hours 80 ℃～100 ℃ following warm air dryings; Halloysite powder, zero(ppm) water and the powdery Sodium hexametaphosphate 99 got after the pulverizing are mixed with mixed solution with mass ratio 1: 10: 0.002～0.01; Stir at normal temperatures after 22～28 hours and left standstill again 70～76 hours; The settled solution of getting behind the standing demix becomes block 80 ℃～100 ℃ following warm air dryings 18～24 hours to halloysite; Block halloysite is pulverized, and crossed 100～200 mesh sieves, obtain nano level pure halloysite powder.
2. the preparation method of the said heat conducting nano composite material of claim 1 is characterized in that, comprises the steps and processing condition:
(1) preparation of nano level halloysite powder
Contained brown in the natural halloysite is partly removed, pulverized after 10～15 hours 80 ℃～100 ℃ following warm air dryings; Halloysite powder, zero(ppm) water and the powdery Sodium hexametaphosphate 99 got after the pulverizing are mixed with mixed solution with mass ratio 1: 10: 0.002～0.01; Stir at normal temperatures after 22～28 hours and left standstill again 70～76 hours; The settled solution of getting behind the standing demix becomes block 80 ℃～100 ℃ following warm air dryings 18～24 hours to halloysite; Block halloysite is pulverized, and crossed 100～200 mesh sieves, obtain nano level pure halloysite powder;
(2) preparation of heat conducting nano composite material: after the material vacuum drying with matrix material, mix, extrude, granulation, injection moulding, make heat conducting nano composite material.
3. the preparation method of heat conducting nano composite material according to claim 2, it is characterized in that: the material vacuum drying of described matrix material is meant that polyamide 66 and thermotropic liquid crystal Vectra A 950 raw materials were 100 ℃～110 ℃ following vacuum-dryings 10～12 hours; Nano level halloysite powder was 90 ℃～100 ℃ following vacuum-dryings 8～10 hours; Ethylene-propylene non-conjugated diene elastomerics grafted maleic anhydride and silicone resin are all 70 ℃～80 ℃ following vacuum-dryings 8～10 hours.
4. the preparation method of heat conducting nano composite material according to claim 2 is characterized in that: extruder barrel mouth temperature is that 250 ℃～260 ℃, transportation section temperature are that 260 ℃～270 ℃, compression section temperature are that 270 ℃～290 ℃, metering zone temperature are 290 ℃～280 ℃; Nozzle temperature is 275 ℃～280 ℃; Screw speed is 180～200r/min; Rate of feeding is 15～20r/min.
5. the preparation method of heat conducting nano composite material according to claim 2 is characterized in that: with granulation in vacuum drying oven behind 100 ℃～110 ℃ down dry 10～12h and under sealing condition, be cooled to room temperature.
6. the preparation method of heat conducting nano composite material according to claim 2 is characterized in that: the used injecting machine material tube mouth temperature of injection moulding is that 250 ℃～260 ℃, transportation section temperature are that 260 ℃～270 ℃, compression section temperature are that 270 ℃～290 ℃, metering zone temperature are 290 ℃～295 ℃; Nozzle temperature is 295 ℃～300 ℃; Die temperature is 80 ℃～100 ℃; Screw speed is 100～120r/min; The injection back pressure is 60～80Mpa.
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| WO2014022963A1 (en) * | 2012-08-07 | 2014-02-13 | Feng Lin | Thermally conductive insulating material of high power led substrate and preparation method therefor |
| CN104098890B (en) * | 2013-04-10 | 2018-08-03 | 上海杰事杰新材料(集团)股份有限公司 | A kind of HPN/TLCP/HNTs composite material and preparation methods |
| CN103694679A (en) * | 2013-12-18 | 2014-04-02 | 上海日之升新技术发展有限公司 | TLCP (Thermotropic Liquid Crystal Polyester)-reinforced conductive TiO2/PA composite material |
| CN107141784A (en) * | 2016-03-01 | 2017-09-08 | 彭昌兰 | Heat conducting nano composite material based on polyamide and preparation method thereof |
| CN112662168B (en) * | 2020-12-04 | 2022-09-09 | 株洲时代工程塑料实业有限公司 | Antibacterial mildew preventive, halogen-free flame-retardant antibacterial mildew-proof nylon composite material, and preparation method and application thereof |
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