CN109575589A - A kind of silicon oxide vesicle reinforced resin based composites and preparation method thereof - Google Patents
A kind of silicon oxide vesicle reinforced resin based composites and preparation method thereof Download PDFInfo
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- CN109575589A CN109575589A CN201811447429.XA CN201811447429A CN109575589A CN 109575589 A CN109575589 A CN 109575589A CN 201811447429 A CN201811447429 A CN 201811447429A CN 109575589 A CN109575589 A CN 109575589A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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Abstract
The invention discloses a kind of silicon oxide vesicle reinforced resin based composites and preparation method thereof.The composite material includes the silicon oxide vesicle that resin base material, additive and surface have hole configurations, the additive and the silicon oxide vesicle are added in the resin base material, the resin base material is filled into the hollow structure of the silicon oxide vesicle, and the silicon oxide vesicle is linked together by the resin base material.
Description
Technical field
The present invention relates to technical field of polymer composite materials, enhance more particularly, to a kind of silicon oxide vesicle and set
Resin-based composite and preparation method thereof.
Background technique
High molecular polymer, especially plastic material are used widely in industries such as automobile, electronics.Plastic material it is light
Quantify, be thinning and have become development trend.But the problems such as following frangible, easily broken, proposes intensity, the rigidity of plastic material
Higher requirement out.
Currently, filling is a kind of important means of material modification；I.e. by filling inorganic filler into high molecular polymer
To achieve the purpose that toughening, reinforcement.
Influence of the selection of filler for the performance of plastic material is most important.For example, being filled out using calcium carbonate, white carbon black etc.
It is unobvious to performance improvements such as intensity, the rigidity of material although cost can be reduced when material is modified material；It uses
Although the fiber-likes such as glass fibre, carbon fiber filler can improve the intensity of material, rigidity, easily there is floating fine, fiber orientation
Product different parts and direction are caused to shrink the problems such as uneven, processing fluidity is poor, toughness of material reduces, product surface is coarse.
Accordingly, it is desirable to provide a kind of new technical solution, to solve the above technical problems.
Summary of the invention
It is an object of the present invention to provide a kind of new solutions of silicon oxide vesicle reinforced resin based composites.
According to the first aspect of the invention, a kind of silicon oxide vesicle reinforced resin based composites, including tree are provided
Aliphatic radical material, additive and surface have the silicon oxide vesicle of hole configurations, and the additive and the silicon oxide vesicle add
It is added in the resin base material, the resin base material is filled into the hollow structure of the silicon oxide vesicle, and described two
Silica vesica is linked together by the resin base material.
Optionally, the resin base material includes polypropylene-based resin, polythylene resin, polystyrene resins, poly- two
Isocyanates resinoid, polyether-ether-ketone resinoid, polyester resin, polyethers ketone resins, polyallyl resinoid, polyformaldehyde class
Resin, polycarbonate resin, polyamide-based resin, polyimide based resin, polysulfones resinoid, polyether sulfone resin, polyethers
Imide resin, polyarylether resinoid, polyurethane based resin, polyethers resinoid, polyaniline compound resin, aromatic ring amides tree
The grafting of the mixture or above-mentioned resin base material of one or more of rouge, multi-metal polypyrrole resin, acrylic resin
Object or copolymer.
Optionally, described hole structure is mesoporous or macropore.
Optionally, the partial size of the silicon oxide vesicle is 20nm-5 μm, wall thickness 3-30nm.
Optionally, it is calculated according to mass fraction, the resin base material is 90-110 parts, and the silicon oxide vesicle is 0.5-
40 parts, the additive is 0.1-6 parts.
Optionally, the additive includes antioxidant, and the antioxidant is phenolic antioxidant, Phosphorus antioxidant, sulphur class are anti-
At least one of oxygen agent, complex type antioxidant.
Optionally, the additive includes lubricant, and the lubricant is fatty acid lubricant, aliphatic amide type profit
Lubrication prescription, ester lubricant, paraffin series lubricant agent, metal soap lubricant, low-molecular-weight wax series lubricant agent and saturated hydrocarbons lubricant
At least one of.
According to the second aspect of the invention, a kind of system of above-mentioned silicon oxide vesicle reinforced resin based composites is provided
Preparation Method, wherein the following steps are included:
Firstly, resin base material is added to progress mixing melting in mixer, temperature is 100-400 DEG C, rotor speed is
20-200rpm, mixing melting time are 1-10min；After mixing melting, silicon oxide vesicle and additive is added, in mixer
In be kneaded, mixing time 2-30min.
The polymer matrix composites being kneaded are carried out extruding pelletization using extruder by second step.
According to one embodiment of the disclosure, dioxy is formed in resin base material using silicon oxide vesicle as filler addition
SiClx vesica reinforced resin based composites can between hollow silica vesica and resin base material with hole configurations
Physics or chemical a variety of interactions are formed, a part of material molecule can penetrate into hollow by the hole configurations of vesica
In structure, so that forming 3 D stereo physics twines contact.In this way, improve polymer matrix composites intensity and just
Property, and make the impact strengths of polymer matrix composites, tensile strength, bending strength, bending modulus while being improved.
Further, since the contact area of silicon oxide vesicle and resin base material increases, material can cause when being impacted
More micro-cracks, therefore more impact energys can be absorbed, resin is improved while keeping polymer matrix composites rigidity
The toughness of based composites.
By referring to the drawings to the detailed description of exemplary embodiment of the present invention, other feature of the invention and its
Advantage will become apparent.
Detailed description of the invention
It is combined in the description and the attached drawing for constituting part of specification shows the embodiment of the present invention, and even
With its explanation together principle for explaining the present invention.
Fig. 1 is the flow chart according to the preparation method of one embodiment of the disclosure.
Specific embodiment
Carry out the various exemplary embodiments of detailed description of the present invention now with reference to attached drawing.It should also be noted that unless in addition having
Body explanation, the unlimited system of component and the positioned opposite of step, numerical expression and the numerical value otherwise illustrated in these embodiments is originally
The range of invention.
Be to the description only actually of at least one exemplary embodiment below it is illustrative, never as to the present invention
And its application or any restrictions used.
Technology, method and apparatus known to person of ordinary skill in the relevant may be not discussed in detail, but suitable
In the case of, the technology, method and apparatus should be considered as part of specification.
It is shown here and discuss all examples in, any occurrence should be construed as merely illustratively, without
It is as limitation.Therefore, other examples of exemplary embodiment can have different values.
It should also be noted that similar label and letter indicate similar terms in following attached drawing, therefore, once a certain Xiang Yi
It is defined in a attached drawing, then in subsequent attached drawing does not need that it is further discussed.
According to one embodiment of the disclosure, a kind of silicon oxide vesicle reinforced resin based composites are provided.This is multiple
Condensation material includes the silicon oxide vesicle that resin base material, additive and surface have hole configurations, the additive and described two
Silica vesica is added in the resin base material, and the resin base material is filled into the hollow structure of the silicon oxide vesicle
In, and the silicon oxide vesicle is linked together by the resin base material.
Optionally, the resin base material includes polypropylene-based resin, polythylene resin, polystyrene resins, poly- two
Isocyanates resinoid, polyether-ether-ketone resinoid, polyester resin, polyethers ketone resins, polyallyl resinoid, polyformaldehyde class
Resin, polycarbonate resin, polyamide-based resin, polyimide based resin, polysulfones resinoid, polyether sulfone resin, polyethers
Imide resin, polyarylether resinoid, polyurethane based resin, polyethers resinoid, polyaniline compound resin, aromatic ring amides tree
The grafting of the mixture or above-mentioned resin base material of one or more of rouge, multi-metal polypyrrole resin, acrylic resin
Object or copolymer.The good fluidity of above-mentioned resin base material can penetrate into the hollow structure of silicon oxide vesicle, resin base
Structural strength is obtained after material solidification.
Optionally, described hole structure is mesoporous or macropore.Mesoporous to refer to aperture in the hole configurations of 2-50nm, macropore is
Finger-hole diameter is greater than the hole configurations of 50nm.Between hollow silica vesica and resin base material, can be formed physics or chemical
A variety of interactions, a part of resin base material can penetrate into hollow structure by the mesoporous or macropore of vesica, form three
It ties up three-dimensional physics and twines contact.Meanwhile there is the silicon oxide vesicle of hole configurations to be scattered in resin matrix on surface, enhance material
Interaction between material and filler, plays humidification, the intensity and rigidity of material can be greatly improved, keep the impact of material strong
Degree, tensile strength, bending strength, bending modulus obtain larger raising simultaneously.
Further, since the contact area of silicon oxide vesicle and resin base material increases, can generate it is more it is crack split, therefore energy
More impact energys are enough absorbed, provide the toughness of resin base material while keeping composite material rigidity.
Specifically, silicon oxide vesicle is usually nanoscale.The partial size of the silicon oxide vesicle is 20nm-5 μm, wall thickness
For 3-30nm.Silicon oxide vesicle is single-wall structure or double-wall structure.Silicon oxide vesicle in the size range makes
The intensity, toughness for obtaining composite material is higher.
In one example, it is calculated according to mass fraction, the resin base material is 90-110 parts, the silicon oxide vesicle
It is 0.5-40 parts, the additive is 0.1-6 parts.In the proportional region, intensity, toughness, the durability of composite material are better
It is good.
Additive is added in resin base material in the form of filler, and is sufficiently mixed, to improve the durable of composite material
The properties such as property, temperature tolerance.
Wherein, the additive includes antioxidant, and the antioxidant is phenolic antioxidant, Phosphorus antioxidant, sulphur class antioxygen
At least one of agent, complex type antioxidant.Above-mentioned antioxidant can effectively improve the ability of composite material anti-oxidant aging,
Keep the durability of composite material more excellent.
Being also possible to the additive includes lubricant, and the lubricant is fatty acid lubricant, aliphatic amide type
Lubricant, ester lubricant, paraffin series lubricant agent, metal soap lubricant, low-molecular-weight wax series lubricant agent and saturated hydrocarbons lubrication
At least one of agent.Lubricant can significantly improve the mobility of resin base material so that resin base material can more rapidly,
It more fully enters in the hollow structure of silicon oxide vesicle.This makes composite material more uniform, and globality is more preferable.
Certainly, additive is not limited to the above embodiments, and can also include light stabilizer, ultraviolet absorbing agent, fire retardant etc.,
Those skilled in the art can be added according to actual needs.
According to another embodiment of the present disclosure, a kind of system of silicon oxide vesicle reinforced resin based composites is provided
Preparation Method comprising following steps:
Resin base material is subjected to pre-fusion.For example, resin base material is added to progress mixing melting in mixer, so that tree
Rouge softening.Preferably, the temperature of mixing melting be 100-400 DEG C, rotor speed 20-200rpm, mixing melting time
For 1-10min.Resin base material can soften melting under this condition.
There is the silicon oxide vesicle of hole configurations and additive to be added in resin base material surface, and further mixes
Refining.Preferably, mixing time 2-30min, under this condition, silicon oxide vesicle and additive can be evenly dispersed in resin
In substrate, composite material has good uniformity.
The polymer matrix composites being kneaded are carried out extruding pelletization using extruder by second step.
Above-mentioned preparation method it is easy to operate, the composite material of formation has good uniformity.
Silicon oxide vesicle is a kind of new packing with hollow structure, has the characteristics that partial size is small, large specific surface area,
Also have the advantages that reduce density polymer in resin base material as filler addition, reduce material utilization amount.In the disclosure, two
Silica vesica has hole configurations.The presence of hole configurations can increase contact area between vesica and resin base material and interface is viscous
Knot property, while generating stress concentration effect.When being stretched effect, due to vesicle surface and surface pit-hole interfacial adhesion
By force, therefore it is able to bear stronger tensile stress.When composite material is hit, due to silicon oxide vesicle filler and resin base material
Contact area increases, can generate it is more it is crack split, more impact energys can be absorbed in this way, keeping composite material rigidity
The toughness of composite material is provided simultaneously.Thus, the present invention enhances high molecular material using the silicon oxide vesicle, to macromolecule
Intensity, rigidity, the toughness of material have carried out preferable enhancing.
Embodiment 1
S11, resin base material (for example, PA66) is dried, resin base material after then weighing the drying (for example,
PA66 1 part of) 100 parts, 10 parts, 1 part antioxidant 1010 of silicon oxide vesicle and lubricant (for example, oleamide), dry energy
Enough effectively remove the moisture of various raw materials；
S12, by the resin base material (for example, PA66) after the drying be added in mixer temperature be 275 DEG C, revolving speed
To carry out mixing melting premix 5min under 80rpm, so that resin softens；And then, by the silicon oxide vesicle, antioxidant
1010, lubricant (for example, oleamide) is added in resin base material (for example, PA66), temperature is 275 DEG C, revolving speed is
Mixing is carried out under 80rpm, and 5min is blended；
After S13, mixing, the resin complexes being kneaded are carried out under the conditions of 275 DEG C using single screw extrusion machine
Extruding pelletization obtains the silicon oxide vesicle reinforced resin based composites.
Embodiment 2
S21, resin base material (for example, PA66) is dried, resin base material after then weighing the drying (for example,
PA66) 90 parts, 15 parts of silicon oxide vesicle, antioxidant 1010 and irgasfos 168 totally 3 parts and lubricant (for example, oleic acid acyl
Amine) 1.5 parts, drying can effectively remove the moisture of various raw materials；
S22, by the resin base material (for example, PA66) after the drying be added in mixer temperature be 275 DEG C, revolving speed
To carry out mixing melting premix 6min under 60rpm, so that resin softens；And then, by the silicon oxide vesicle, antioxidant,
Lubricant (for example, oleamide) be added to mixing melting resin base material in, in the case where temperature is 275 DEG C, revolving speed is 60rpm into
7min is blended in row mixing；
After S23, mixing, the resin complexes being kneaded are carried out under the conditions of 275 DEG C using single screw extrusion machine
Extruding pelletization obtains the silicon oxide vesicle reinforced resin based composites.
Embodiment 3
S31, resin base material (for example, PP) is dried, the resin base material (for example, PP) after then weighing the drying
3 parts of 110 parts, 7 parts, 0.5 part antioxidant 1010 of silicon oxide vesicle and lubricant (for example, erucyl amide and paraffin oil) are done
The dry moisture that can effectively remove various raw materials；
S32, the resin base material (for example, PP) after the drying is added in mixer temperature is 180 DEG C, revolving speed is
After carrying out mixing melting premix 5min under 60rpm, so that resin softens；And then, by the silicon oxide vesicle, antioxidant,
Lubricant (for example, erucyl amide and paraffin oil) is added in the resin base material of mixing melting, temperature is 180 DEG C, revolving speed is
Mixing is carried out under 60rpm, and 4min is blended；
After S33, mixing, the resin complexes being kneaded are carried out under the conditions of 180 DEG C using single screw extrusion machine
Extruding pelletization obtains the silicon oxide vesicle reinforced resin based composites.
Embodiment 4
S41, resin base material (for example, PC/ABS) is dried, the resin base material (example after then weighing the drying
Such as, PC/ABS) 100 parts, 1 part of 5 parts, 1 part antioxidant 1076 of silicon oxide vesicle and lubricant (for example, oleamide), it does
The dry moisture that can effectively remove various raw materials；
S42, by the resin base material (for example, PC/ABS) after the drying be added in mixer temperature be 240 DEG C, turns
Speed is that mixing melting premix 3min is carried out under 80rpm, so that resin softens；And then, by the silicon oxide vesicle, antioxygen
Agent, lubricant (for example, oleamide) are added in the resin base material (for example, PC/ABS) of mixing melting, are 240 in temperature
DEG C, revolving speed be 80rpm under carry out mixing be blended 5min；
After S43, mixing, the resin complexes being kneaded are carried out under the conditions of 240 DEG C using single screw extrusion machine
Extruding pelletization obtains the silicon oxide vesicle reinforced resin based composites.
Embodiment 5
S51, resin base material (for example, PC) is dried, 100 parts of resin base material after then weighing the drying, two
0.7 part of 40 parts, 0.1 part irgasfos 168 of silica vesica and lubricant (for example, ethylene bis stearamide), drying can have
Effect removes the moisture of various raw materials；
S52, the resin base material (for example, PC) after the drying is added in mixer temperature is 255 DEG C, revolving speed is
Mixing melting premix 10min is carried out under 200rpm, so that resin softens；And then, by the silicon oxide vesicle, antioxidant,
Lubricant (for example, ethylene bis stearamide) be added to mixing melting resin base material (for example, PC) in, temperature be 255 DEG C,
Revolving speed is to carry out mixing under 100rpm 5min is blended；
After S53, mixing, the resin complexes being kneaded are carried out under the conditions of 255 DEG C using single screw extrusion machine
Extruding pelletization obtains the silicon oxide vesicle reinforced resin based composites.
Embodiment 6
S61, resin base material (for example, PBT) is dried, resin base material after then weighing the drying (for example,
PBT 0.1 part of) 100 parts, 20 parts, 0.7 part irgasfos 168 of silicon oxide vesicle and lubricant (for example, oleamide), it is dry
The moisture of various raw materials can be effectively removed；
S62, by the resin base material (for example, PBT) after the drying be added in mixer temperature be 260 DEG C, revolving speed
To carry out mixing melting premix 5min under 20rpm, so that resin softens；And then, by the silicon oxide vesicle, antioxidant,
Lubricant (for example, oleamide) is added in the resin base material (for example, PBT) of mixing melting, is 260 DEG C, revolving speed in temperature
2min is blended to carry out mixing under 100rpm；
After S63, mixing, the resin complexes being kneaded are carried out under the conditions of 260 DEG C using single screw extrusion machine
Extruding pelletization obtains the silicon oxide vesicle reinforced resin based composites.
Embodiment 7
S71, resin base material (for example, ABS) is dried, resin base material after then weighing the drying (for example,
ABS 1 part of) 100 parts, 7 parts of silicon oxide vesicle, 1 part of antioxidant (for example, TNPP) and lubricant (for example, erucyl amide) are done
The dry moisture that can effectively remove various raw materials；
S72, by the resin base material (for example, ABS) after the drying be added in mixer temperature be 220 DEG C, revolving speed
To carry out mixing melting premix 1min under 80rpm, so that resin softens；And then, by the silicon oxide vesicle, antioxidant,
Lubricant (for example, erucyl amide) is added in the resin base material (for example, ABS) of mixing melting, is 220 DEG C, revolving speed in temperature
30min is blended to carry out mixing under 20rpm；
After S73, mixing, the resin complexes being kneaded are carried out under the conditions of 220 DEG C using single screw extrusion machine
Extruding pelletization obtains the silicon oxide vesicle reinforced resin based composites.
Embodiment 8
S81, resin base material (for example, PPS) is dried, resin base material after then weighing the drying (for example,
PPS) 90 parts, 0.5 part of silicon oxide vesicle, antioxidant 1010 and irgasfos 168 totally 1.4 parts and lubricant (for example, stearic acid
Zinc and calcium stearate) 1.4 parts, drying can effectively remove the moisture of various raw materials；
S82, by the resin base material (for example, PPS) after the drying be added in mixer temperature be 295 DEG C, revolving speed
To carry out mixing melting premix 5min under 80rpm, so that resin softens；And then, by the silicon oxide vesicle, antioxidant,
Lubricant is added in the resin base material (for example, PPS) of mixing melting, is carried out in the case where temperature is 295 DEG C, revolving speed is 80rpm close
5min is blended in refining；
After S83, mixing, the resin complexes being kneaded are carried out under the conditions of 295 DEG C using single screw extrusion machine
Extruding pelletization obtains the silicon oxide vesicle reinforced resin based composites.
The mechanical property of silicon oxide vesicle reinforced resin based composites made from embodiment 1-8 is as shown in table 1:
Table 1:
After tested, it is seen that the silicon oxide vesicle reinforced resin based composites that above-mentioned preparation method is prepared have good
Good rigidity, toughness and impact strength.
Although some specific embodiments of the invention are described in detail by example, the skill of this field
Art personnel it should be understood that example above merely to being illustrated, the range being not intended to be limiting of the invention.The skill of this field
Art personnel are it should be understood that can without departing from the scope and spirit of the present invention modify to above embodiments.This hair
Bright range is defined by the following claims.
Claims (8)
1. a kind of silicon oxide vesicle reinforced resin based composites, wherein there is hole including resin base material, additive and surface
The silicon oxide vesicle of hole structure, the additive and the silicon oxide vesicle are added in the resin base material, the tree
Aliphatic radical material is filled into the hollow structure of the silicon oxide vesicle, and the silicon oxide vesicle passes through the resin base material
It links together.
2. silicon oxide vesicle reinforced resin based composites according to claim 1, wherein the resin base material includes
Polypropylene-based resin, polystyrene resins, poly- diisocyanate resinoid, polyether-ether-ketone resinoid, gathers polythylene resin
Esters resin, polyethers ketone resins, polyallyl resinoid, polyformaldehyde resinoid, polycarbonate resin, polyamide-based tree
Rouge, polyimide based resin, polysulfones resinoid, polyether sulfone resin, polyetherimide resinoid, polyarylether resinoid, poly- ammonia
Esters resin, polyethers resinoid, polyaniline compound resin, aromatic ring amide resinoid, multi-metal polypyrrole resin, in acrylic resin
One or more kinds of mixtures or above-mentioned resin base material graft or copolymer.
3. silicon oxide vesicle reinforced resin based composites according to claim 1, wherein described hole structure is to be situated between
Hole or macropore.
4. silicon oxide vesicle reinforced resin based composites according to claim 3, wherein the silicon oxide vesicle
Partial size be 20nm-5 μm, wall thickness 3-30nm.
5. silicon oxide vesicle reinforced resin based composites according to claim 1, wherein according to mass fraction meter
It calculates, the resin base material is 90-110 parts, and the silicon oxide vesicle is 0.5-40 parts, and the additive is 0.1-6 parts.
6. silicon oxide vesicle reinforced resin based composites according to claim 1, wherein the additive includes anti-
Oxygen agent, the antioxidant are at least one of phenolic antioxidant, Phosphorus antioxidant, sulfur type antioxidant, complex type antioxidant.
7. silicon oxide vesicle reinforced resin based composites according to claim 1, wherein the additive includes profit
Lubrication prescription, the lubricant are fatty acid lubricant, aliphatic amide series lubricant agent, ester lubricant, paraffin series lubricant agent, gold
Belong at least one of soaps lubricant, low-molecular-weight wax series lubricant agent and saturated hydrocarbons lubricant.
8. a kind of preparation method of silicon oxide vesicle reinforced resin based composites, wherein the following steps are included:
It is carried out firstly, resin base material is added in mixer in the case where temperature is 100-400 DEG C, rotor speed is 20-200rpm
Mixing melting, mixing melting time are 1-10min；After mixing melting, silicon oxide vesicle and additive is added, in mixer
It is kneaded, mixing time 2-30min；
Then, the polymer matrix composites being kneaded are subjected to extruding pelletization using extruder.
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Citations (4)
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|---|---|---|---|---|
| CN101289189A (en) * | 2008-04-03 | 2008-10-22 | 复旦大学 | Earth silicon vesicle material with controllable shape, dimension and thickness of wall and method for preparing same |
| CN101857234A (en) * | 2010-06-10 | 2010-10-13 | 天津大学 | Monodisperse mesoporous silicon dioxide hollow nano-microsphere and preparation method |
| US20130034609A1 (en) * | 2010-02-09 | 2013-02-07 | Agency For Science, Technology And Research | Smart polymers functionalized hollow silica vesicles |
| CN105980447A (en) * | 2013-12-19 | 2016-09-28 | 昆士兰大学 | Method of synthesis of silica vesicles and use thereof |
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2018
- 2018-11-29 CN CN201811447429.XA patent/CN109575589A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289189A (en) * | 2008-04-03 | 2008-10-22 | 复旦大学 | Earth silicon vesicle material with controllable shape, dimension and thickness of wall and method for preparing same |
| US20130034609A1 (en) * | 2010-02-09 | 2013-02-07 | Agency For Science, Technology And Research | Smart polymers functionalized hollow silica vesicles |
| CN101857234A (en) * | 2010-06-10 | 2010-10-13 | 天津大学 | Monodisperse mesoporous silicon dioxide hollow nano-microsphere and preparation method |
| CN105980447A (en) * | 2013-12-19 | 2016-09-28 | 昆士兰大学 | Method of synthesis of silica vesicles and use thereof |
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| 吴湘锋: ""空心微珠的制备及其高强轻质树脂基复合材料的结构与性能研究"", 《中国博士学位论文全文数据库 工程科技I辑》 * |
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