CN1286909C - Process for preparing four-leg zinc-oxide crystal whisker reinforced epoxy composite materials - Google Patents
Process for preparing four-leg zinc-oxide crystal whisker reinforced epoxy composite materials Download PDFInfo
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- CN1286909C CN1286909C CN 200510045897 CN200510045897A CN1286909C CN 1286909 C CN1286909 C CN 1286909C CN 200510045897 CN200510045897 CN 200510045897 CN 200510045897 A CN200510045897 A CN 200510045897A CN 1286909 C CN1286909 C CN 1286909C
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Abstract
The present invention provides a simple preparation method of novel reinforced epoxy composite materials with quadruped-shaped zinc oxide crystal whiskers, which comprises the following steps: firstly, pretreating quadruped-shaped zinc oxide crystal whiskers with propanone or petroleum ether solution of a coupling agent under a condition of ultrasonic wave; adding the pretreated quadruped-shaped zinc oxide crystal whiskers to epoxy resin which is preheated to 50 to 70 DEG C; dispersing the pretreated quadruped-shaped zinc oxide crystal whiskers and the epoxy resin after being mechanically stirred; deaerating the dispersed mixture for 10 to 50 minutes; then, adding a certain amount of curing agent to the mixture and uniformly stirred the mixture; deaerating the mixture with ultrasonic wave and pouring the deaerated mixture in a mould which is preheated to 90 DEG C. The mixture poured in the mould is thermally cured or cured at room temperature under the condition of vacuum pumping for several hours. The reinforced epoxy composite materials with the quadruped-shaped crystal whiskers are obtained after the mixture is cured completely and the mould is unloaded. The preparation method has the advantage of simple operation, the intensity and the toughness of the prepared epoxy composite materials are increased simultaneously, and the epoxy composite material has a function of resisting static electricity. In addition, the novel reinforced epoxy composite materials with quadruped-shaped zinc oxide crystal whiskers have wide industrial application prospects.
Description
Technical field
The present invention relates to preparation of a kind of novel material and production field, particularly a kind of simple and easy, preparation method cheaply of four-leg crystal whisker of zinc oxide reinforced epoxy matrix material.
Background technology
Resins, epoxy is a kind of important thermosetting resin, has advantages such as good mechanical property, electric property, cementability, chemical proofing, thermotolerance and dimensional stability.Be widely used in fields such as machinery, space flight and aviation, light industry, building, tackiness agent, coating.But the cross-linking density height is tridimensional network behind the epoxy resin cure, exists bigger internal stress, has that matter is crisp, resistance to fatigue, a humidity resistance difference and easily produce shortcoming such as static, has limited the application in some high-tech area largely.Therefore, to the enhancing of Resins, epoxy, toughness reinforcing be the heat subject that people study always.Many scientific research personnel have made effort for this reason, to increase its toughness, improve the using value of Resins, epoxy.
At present, TOUGHENING MODIFICATION OF EPOXY RESINS there are a lot of methods.CN86108464A (1988) has described the toughness reinforcing method of a kind of butyronitrile hydroxyl, promptly in 100 parts of bisphenol A type epoxy resins, add 5～60 parts of terminal hydroxy group perbutans, 5～100 parts of anhydride curing agents and 0～6 part of tertiary amine catalyst, solidified 10～100 hours down at 50～160 ℃, prepared epoxy resin toughened matrix material.CN1033523A (1989) discloses the epoxy resin toughened method of a kind of ending carboxy polyurethane.Someone has delivered with unsaturated polyester and vinyl monomer and directly carried out in situ polymerization in Resins, epoxy, makes the method for the dispersion of stable microgel in Resins, epoxy and comes epoxy resin toughened CN1059733A (1992).Someone has invented CN1083497A (1994) patent, and it is epoxy resin toughened to prepare toughner with TLCP and thermoplastic molten wire drawing.Recently, the someone has reported that original position and parcel polymerization prepare the technology CN1417246A (2003) of nanoparticle/epoxy resin composite material.Although method for toughening is a lot, effect is also comparatively obvious, and what majority adopted is the method for the toughness reinforcing stiffening ring epoxy resins of flexible molecule.Its weak point is: method is loaded down with trivial details, need carry out chemical reaction and realize; The dimensional stability of Resins, epoxy descends to some extent because of the introducing of flexible molecule; Cost is higher; Epoxy-resin systems body viscosity is bigger, easily produces microbubble when casting, makes the performance difficulty of material reach desirable index, and introduce flexible molecule system viscosity is further increased; Difficult realization strengthens simultaneously with toughness reinforcing.
Summary of the invention
Simple and easy, the preparation method cheaply that the purpose of this invention is to provide a kind of four-leg crystal whisker of zinc oxide reinforced epoxy matrix material.
The objective of the invention is to be achieved through the following technical solutions:
The preparation method of four-leg crystal whisker of zinc oxide reinforced epoxy matrix material, with acetone or petroleum ether solution under ultrasonic wave condition the pre-treatment of four-leg crystal whisker of zinc oxide with coupling agent, join in the Resins, epoxy that has been preheated to 50～70 ℃ more in proportion, after the mechanical stirring, use ultrasonic dispersing, deaeration 10～50 minutes again; Then, add a certain amount of solidifying agent, stir, be poured into then in the mould that is preheating to 90 ℃; Under situation about vacuumizing, be heating and curing or self-vulcanizing a few hours, after the completely solidified, die sinking promptly obtains four-leg crystal whisker of zinc oxide reinforced epoxy matrix material.
109 ° of every pins of the angle of any two pins of whisker are about 40～80 μ m, and base diameter is 2.0～3.0 μ m, and length-to-diameter ratio is 20～40.0.5 the weight of～6% Resins, epoxy.
Used coupling agent and method are: the acetone of silicane and titante coupling agent or petroleum ether solution, coupling agent consumption are 0.5～3% of four-leg crystal whisker of zinc oxide weight; Used dispersing method is a supersonic method; Used coupling agent can be selected silane coupling agent for use.
Adopt ultrasonic dispersing, deaeration pouring technology in the poured with epoxy resin.
Advantage of the present invention and effect are:
Preparation technology is simple and easy, low-cost; Using ultrasonic technology disperses, deaeration, makes the coupling pre-treatment more even, effective, reaches the bubble that is produced when eliminating poured with epoxy resin, reduces the subsurface defect of material.High temperature curing systems such as ambient cures such as the present invention does not have particular requirement to the Resins, epoxy type, and curing system is not had particular requirement, polyamine and acid anhydrides all can.The intensity and the toughness of Resins, epoxy are improved simultaneously, and have anti-static function, and this matrix material can be widely used in fields such as machinery, space flight and aviation, light industry, building, tackiness agent, coating.
Description of drawings
Fig. 1 is: the four-leg crystal whisker of zinc oxide photo;
Fig. 2 is: the impact fracture photo that does not add the epoxy resin composite material of four-leg crystal whisker of zinc oxide;
Fig. 3 is: the impact fracture photo that adds the epoxy resin composite material of four-leg crystal whisker of zinc oxide.
Embodiment
The present invention is described in further detail below in conjunction with example.
Embodiment 1
At first, take by weighing the 0.75g four-leg crystal whisker of zinc oxide, take by weighing NDZ-401 type titante coupling agent by 1% of four-leg crystal whisker of zinc oxide mass ratio, it is dissolved in the sherwood oil, be made into dilute solution, pour in the load weighted four-leg crystal whisker of zinc oxide, disperseed 60 minutes with ultrasonic wave (frequency is 99HZ) down in 70 ℃, after treating that solvent evaporates fully, drying promptly got the four-leg crystal whisker of zinc oxide of handling well in two hours in 110 ℃ baking oven.
Extracting epoxy resin (E-44) 125g adds surface treated four-leg crystal whisker of zinc oxide in the Resins, epoxy (being preheated to 70 ℃), after the mechanical stirring, uses ultrasonic dispersing again 30 minutes.Then, add the trolamine solidifying agent of 12% (massfraction), stir, ultrasonic wave froth breaking 10 minutes is poured in the mould that has been preheating to 90 ℃ then.Under situation about vacuumizing, after being heating and curing 1 hour, be warming up to 120 ℃ again and be heating and curing 2 hours, stop heating, cool to room temperature, die sinking with the furnace, promptly get required epoxy composite material sample.The epoxy resin composite material performance see Table 1.
Comparative example 1
Take by weighing Resins, epoxy (E-44) 125g (being preheated to 70 ℃), after mechanical stirring is even.Add the trolamine solidifying agent of 12% (massfraction), stir, be poured into then in the mould that is preheating to 90 ℃.Under situation about vacuumizing, after being heating and curing 1 hour, be warming up to 120 ℃ again and be heating and curing 2 hours, stop heating, cool to room temperature, die sinking with the furnace, promptly get required epoxy material sample.The Resins, epoxy performance see Table 1.
Embodiment 2
Take by weighing the four-leg crystal whisker of zinc oxide of 7.50g, take by weighing KH550 type silane coupling agent by 2% of four-leg crystal whisker of zinc oxide mass ratio, it is dissolved in the acetone, be made into dilute solution, pour in the load weighted four-leg crystal whisker of zinc oxide, disperseed 60 minutes down in 70 ℃ with ultrasonic wave (frequency is 99HZ), treat that solvent evaporates fully after, drying promptly got the four-leg crystal whisker of zinc oxide of handling well in two hours in 110 ℃ baking oven.
Extracting epoxy resin (E-44) 125g adds surface treated four-leg crystal whisker of zinc oxide in the Resins, epoxy (being preheated to 70 ℃), after the mechanical stirring, uses ultrasonic dispersing again 30 minutes.Then, add the trolamine solidifying agent of 12% (massfraction), stir, ultrasonic wave froth breaking 10 minutes is poured in the mould that has been preheating to 90 ℃ then.Under situation about vacuumizing, after being heating and curing 1 hour, be warming up to 120 ℃ again and be heating and curing 2 hours, stop heating, cool to room temperature, die sinking with the furnace, promptly get required epoxy composite material sample.The epoxy resin composite material performance see Table 1.
Embodiment 3
Take by weighing the four-leg crystal whisker of zinc oxide of 0.625g, take by weighing NDZ-401 type titante coupling agent by 2% of four-leg crystal whisker of zinc oxide mass ratio, it is dissolved in the sherwood oil, be made into dilute solution, pour in the load weighted four-leg crystal whisker of zinc oxide, disperseed 60 minutes down in 70 ℃ with ultrasonic wave (frequency is 99HZ), treat that solvent evaporates fully after, drying promptly got the four-leg crystal whisker of zinc oxide of handling well in two hours in 110 ℃ baking oven.
Extracting epoxy resin (E-44) 125g adds surface treated four-leg crystal whisker of zinc oxide in the Resins, epoxy (being preheated to 70 ℃), after the mechanical stirring, uses ultrasonic dispersing again 30 minutes.Then, add the methyl tetrahydrochysene anhydride curing agent of 20% (massfraction), stir, ultrasonic wave froth breaking 10 minutes is poured in the mould that has been preheating to 90 ℃ then.Under situation about vacuumizing, after being heating and curing 1 hour, be warming up to 120 ℃ again and be heating and curing 2 hours, stop heating, cool to room temperature, die sinking with the furnace, promptly get required epoxy composite material sample.The Resins, epoxy composite performance see Table 1.
The epoxide resin material (comparative example 1) and the impact fracture photo of the epoxy resin composite material (embodiment 1) that adds four-leg crystal whisker of zinc oxide are observed, as shown in Figures 2 and 3:
From figure as can be seen: strengthen toughness reinforcing after, the section of matrix material is coarse than the sample of comparative example 1, from microcosmic, crackle is more careful.Epoxy resin composite material is a kind of hard brittle material, and the surface of fracture after it destroys is slick, fibrous surfaces that immalleable fracture presented or dimple.By the observation of scanning electron microscope, can find that crack morphology is the river sample on the surface of fracture, belong to cleavage fracture.Toughness reinforcing front and back, the degree of roughness of crackle changes to some extent.The increase of crackle, the densification of tractive structure, matrix viscous deformation more obvious can be as judging the toughness reinforcing foundation of material.T-ZnO whisker with semiconductive is in matrix material, and overlap joint forms conductive path mutually, with valence band conduction pattern conduct charges, and plays antistatic property, makes the surface resistivity of epoxide resin material reduce by 9 orders of magnitude.
The performance of table 1 epoxy resin composite material
| Epoxy resin composite material | Tensile strength MPa | Shock strength kg.cm/cm | Surface resistivity 10 12Ω.cm |
| Embodiment 1 | 27.07 | 6.53 | 11 |
| Comparative example 1 | 23.50 | 2.50 | 3700 |
| Embodiment 2 | 39.70 | 11.66 | 0.000001 |
| Embodiment 3 | 38.50 | 10.75 | 0.000053 |
Preparation were established of the present invention is:
(1) the four-leg crystal whisker of zinc oxide (see figure 1) is carried out the coupling pre-treatment with the acetone or the petroleum ether solution of coupling agent (consumption four-leg crystal whisker of zinc oxide weight 0.5～3%) under the ultrasonic wave condition, coupling agent can be silicane and titanate ester;
(2) add in proportion in the Resins, epoxy (50～70 ℃ of preheatings), after the mechanical stirring, use ultrasonic dispersing, deaeration 10～50 minutes again;
(3) then, add a certain amount of solidifying agent, stir, be poured into then in the mould that is preheating to 90 ℃.Under situation about vacuumizing, be heating and curing or self-vulcanizing a few hours;
(4) after the completely solidified, die sinking promptly gets four-leg crystal whisker of zinc oxide reinforced epoxy matrix material.
Claims (5)
1. the preparation method of four-leg crystal whisker of zinc oxide reinforced epoxy matrix material, it is characterized in that: with acetone or petroleum ether solution under ultrasonic wave condition the pre-treatment of four-leg crystal whisker of zinc oxide with coupling agent, join in the Resins, epoxy that has been preheated to 50～70 ℃ more in proportion, after the mechanical stirring, use ultrasonic dispersing, deaeration 10～50 minutes again; Then, add a certain amount of solidifying agent, stir, be poured into then in the mould that is preheating to 90 ℃; Under situation about vacuumizing, be heating and curing or self-vulcanizing a few hours, after the completely solidified, die sinking promptly obtains four-leg crystal whisker of zinc oxide reinforced epoxy matrix material.
2. according to the preparation method of the described four-leg crystal whisker of zinc oxide reinforced epoxy of claim 1 matrix material, it is characterized in that: 109 ° of every pins of the angle of any two pins of four-leg crystal whisker of zinc oxide are about 40～80 μ m, base diameter is 2.0～3.0 μ m, and length-to-diameter ratio is 20～40.
3. according to the preparation method of the described four-leg crystal whisker of zinc oxide reinforced epoxy of claim 1 matrix material, it is characterized in that: the four-leg crystal whisker of zinc oxide consumption is the weight 0.5～6% of Resins, epoxy.
4. according to the preparation method of the described four-leg crystal whisker of zinc oxide reinforced epoxy of claim 1 matrix material, it is characterized in that: through the four-leg crystal whisker of zinc oxide of coupling processing, used coupling agent and method are the acetone or the petroleum ether solution of silicane and titante coupling agent, and the coupling agent consumption is 0.5～3% of a four-leg crystal whisker of zinc oxide weight; Used dispersing method is a supersonic method; Used coupling agent is selected silane coupling agent for use.
5. according to the preparation method of the described four-leg crystal whisker of zinc oxide reinforced epoxy of claim 1 matrix material, it is characterized in that: adopt ultrasonic dispersing, deaeration pouring technology in the poured with epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 200510045897 CN1286909C (en) | 2005-02-23 | 2005-02-23 | Process for preparing four-leg zinc-oxide crystal whisker reinforced epoxy composite materials |
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| CN 200510045897 CN1286909C (en) | 2005-02-23 | 2005-02-23 | Process for preparing four-leg zinc-oxide crystal whisker reinforced epoxy composite materials |
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| CN1667041A CN1667041A (en) | 2005-09-14 |
| CN1286909C true CN1286909C (en) | 2006-11-29 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101423618B (en) * | 2008-12-19 | 2011-05-11 | 中国航空工业第一集团公司北京航空材料研究院 | Method for preparing rigid three-dimensional crystal whisker interlayer modified continuous fiber composite material |
| CN104945846B (en) * | 2015-05-14 | 2016-08-17 | 西安交通大学 | A kind of preparation method of high voltage earial drainage protection packaging material |
| CN109135182B (en) * | 2017-06-16 | 2022-06-17 | 合肥杰事杰新材料股份有限公司 | Preparation method of thermosetting epoxy resin with shape memory performance |
| CN108395143A (en) * | 2018-02-09 | 2018-08-14 | 同济大学 | A kind of high intensity sand base water-permeable brick and preparation method thereof with heating function |
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