CN104448719B - Organic and inorganic hollow microsphere compounded deepwater buoyancy material and preparation method thereof - Google Patents
Organic and inorganic hollow microsphere compounded deepwater buoyancy material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 80
- 239000004005 microsphere Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000011521 glass Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000011806 microball Substances 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 8
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- -1 polyethylene Polymers 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 18
- 238000001514 detection method Methods 0.000 abstract description 6
- 238000007906 compression Methods 0.000 abstract description 5
- 230000006835 compression Effects 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 description 17
- 238000000034 method Methods 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000007493 shaping process Methods 0.000 description 7
- 230000002706 hydrostatic effect Effects 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 239000003999 initiator Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000002596 correlated effect Effects 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000013036 cure process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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Abstract
The invention provides an organic and inorganic hollow microsphere compounded deepwater buoyancy material and a preparation method thereof. The material is prepared from the following components in parts by mass: 100 parts of unsaturated resin, 2-4 parts of a curing agent, 0.5-2 parts of an accelerant, 10-15 parts of organic hollow microspheres and 40 parts of inorganic hollow microspheres. The invention provides the buoyancy material which provides buoyancy to an underwater device for ocean deepwater detection, ocean development and related use. The buoyancy material is low in density, high in strength and excellent in machinable property. The density of the prepared deepwater buoyancy material is 0.40-0.45g/cm<3> and the compression strength is 30-35MPa, so that the buoyancy material meets the request for deepwater universal materials.
Description
Technical field
A kind of a kind of the present invention relates to buoyant material, the present invention also relates to preparation method of buoyant material.Specifically
Say it is buoyant material and its preparation that a kind of underwater units for ocean deepwater detection, ocean development and associated uses provide buoyancy
Method.
Background technology
Growing to natural resources demand with people, land resources is day by day exhausted, and people have turned one's attention to money
The marine field that source is enriched.Benthos widely distributed the oceanic multi-metal nodule of multiple element, submarine oil and natural gas
Reserves account for the 45% of world's total amount.The resource wanting to develop and detect at deep water be unable to do without marine settings, and deep-sea ocean dress
The standby net buoyancy needing buoyant material offer enough.The density of deep water buoyant material and the size of compressive resistance, directly determine
The service behaviour of deep sea equipment and working depth.How to reduce the density of deep water buoyant material, improve deep water buoyant material intensity
Research be increasingly subject to people's attention.
The deep-sea both domestic and external buoyant material overwhelming majority all adopts resin at present is matrix, fills inorganic hollow microspheres to drop
Low-density, but the restriction being filled with maximum filling proportion of inorganic hollow microspheres, although density is permissible after exceeding maximum packing ratio
Continue reduce, but resin can not fully wrapped around inorganic hollow microspheres, resin is with the interface cohesion of inorganic hollow microspheres simultaneously
Poor-performing, the buoyant material compressive resistance of final preparation is very low, and has higher water absorption rate.Publication No. cn103665758
Patent document in, disclose a kind of preparation method of High-strength solid buoyancy material, it is fine that the method adopts tiny balloon to add
Dimension bead prepares buoyant material, and such material can be applicable to 3000 meters of depth of waters, but its density is more than 0.5g/cm3, long service suction
Water rate is higher.A kind of solid buoyancy of chemical blowing process preparation is described in the patent document of Application No. 200410030821.6
Material, density of material is less than 0.33g/cm3, compression strength only 5.5mpa is it is impossible to be applied to 1000m with headwater depth.Application number
Normal using glass microballoon filling unsaturated-resin in patent application document for 201010552911.7 and 201310065622.8
Temperature prepares buoyant material, but the buoyant material density of its preparation is less than 0.45g/cm3Shi Qiangdu is respectively less than 13mpa, and intensity is more than
During 30mpa, density is all higher than 0.56g/cm3.File disclosed above is not all reported and be can be applicable to more than depth of water 2000m, compressive resistance
More than 30mpa, density is less than 0.45g/cm3Normal temperature preparation deep water buoyant material.
Content of the invention
It is an object of the invention to provide the organic and inorganic hollow that a kind of density is low, intensity is high, processability is excellent
The deep water buoyant material that microballoon compounds.The present invention also aims to provide a kind of, moulding process relatively low to equipment requirement simple,
The preparation method of the deep water buoyant material that the organic and inorganic hollow microspheres of low cost compound.
The deep water buoyant material that the organic and inorganic hollow microspheres of the present invention compound is unsaturated-resin by quality parts ratio
100 parts, 2～4 parts of curing agent, 0.5～2 part of accelerator, 10～15 parts of organic tiny balloon and 40 parts of compositions of inorganic hollow microspheres.
Described organic tiny balloon is hollow structure, and particle diameter is 20 μm, and density is 0.15g/cm3Macromolecule organic micro-
Ball.
Described macromolecule organic micro-spheres are hollow epoxide resin microballoon and/or polyethylene tiny balloon.
Described inorganic hollow microspheres are particle diameters is 80 μm, and density is 0.3g/cm3Hollow glass micro-ball.
Described hollow glass micro-ball hollow be filled with air or be vacuum.
Described unsaturated-resin is epoxy vingl ester resin.Described curing agent selects methyl ethyl ketone peroxide as initiator.
Described accelerator selects cobalt naphthenate or cobalt iso-octoate accelerator.
The preparation method of the deep water buoyant material that the organic and inorganic hollow microspheres of the present invention compound is:
(1) in terms of mass fraction, take 100 parts of unsaturated-resin, 2～4 parts of curing agent, 0.5～2 part of accelerator, add anti-
Answer in kettle, be uniformly mixed with stirring rod, obtain resin adhesive liquid；
(2) in terms of mass fraction, 10～15 parts of organic tiny balloon and 40 parts of addition vacuum stirring of inorganic hollow microspheres are taken
In machine, mix and obtain mixing microballoon；
(3) described resin adhesive liquid is added in described mixing microballoon, vacuum stirring, mixing speed 25r/min, during stirring
Between 40min, mix and obtain mixed material；
(4) described mixed material is put in vacuum drying chamber, normal-temperature vacuum deaeration；
(5) it is poured in mould, normal temperature cure is molded.
The present invention provides a kind of buoyancy of buoyancy for the underwater units of ocean deepwater detection, ocean development and associated uses
Material, this buoyant material is the excellent deep water buoyant material of a kind of low-density, high intensity, processability.It is mainly characterized by
A kind of deep water buoyant material compounding preparation with organic tiny balloon and inorganic hollow microspheres.
The main feature of the preparation method of the present invention has: organic hollow glass micropearl is mixed with inorganic hollow microballon stirring at low speed
Legal.Unsaturated-resin selects epoxy vingl ester resin；Normal temperature cured type curing agent selected by curing agent, and this normal temperature cured type solidifies
Agent is methyl ethyl ketone peroxide；Accelerator is cobalt naphthenate or cobalt iso-octoate；Organic tiny balloon be hollow epoxide resin microballoon and/
Or polyethylene tiny balloon, the particle diameter of selection is 20 μm, and density is 0.15g/cm3；Inorganic hollow microspheres are hollow glass micro-ball,
The particle diameter that this hollow glass microballoon is selected is 80 μm, and density is 0.3g/cm3.The present invention pass through each material composition reasonably combined,
By suitable technological process, the deep water buoyant material density of preparation is relatively low, is 0.40 to 0.45g/cm3；Compressive resistance 30 to
35mpa, meets the universal material requirements in deep-sea.This forming method of the present invention is relatively low to equipment requirement, and moulding process is simple, becomes
This is low.
Specific embodiment
Illustrate below and the present invention is described in more detail.
Embodiment 1:
Compound according to table 1 proportioning organic/inorganic tiny balloon respectively and prepare deep water buoyant material, concrete preparation method is:
(1) in terms of mass fraction, take 100 parts of unsaturated-resins, 2 parts, 1 part accelerator of curing agent to add in reactor, mix
Close uniformly, obtain resin adhesive liquid；
(2) in terms of mass fraction, 10 parts of organic tiny balloons, 40 parts of inorganic hollow microspheres are taken to add in de-airing mixer,
Mix；
(3) will obtain in the resin adhesive liquid that obtain in above-mentioned steps 1 and step 2 mixing tiny balloon addition vacuum stirring
In machine, vacuum stirring, mixing speed 25r/min, mixing time 40min, mix；
(4) mixed material obtaining in above-mentioned steps 3 is put in vacuum drying chamber, vacuum defoamation under normal temperature；
(5) material obtaining above-mentioned steps 4 is poured in various moulds, by normal temperature cure shaping.
Table 1 organic/inorganic tiny balloon compounds prepares deep water buoyant material parts by weight of component
| Epoxy vingl ester resin | Curing agent | Initiator | Organic tiny balloon | Inorganic hollow microspheres | |
| Embodiment 1 | 100 | 2 | 1 | 10 | 40 |
In Table 1: methyl ethyl ketone peroxide selected by curing agent；Accelerator selects cobalt naphthenate or cobalt iso-octoate；Organic hollow
Microballoon is hollow epoxide resin microballoon and/or polyethylene tiny balloon, and the particle diameter of selection is 20 μm, and density is 0.15g/cm3；Institute
Stating inorganic hollow microspheres is hollow glass micro-ball, and the particle diameter that this hollow glass microballoon is selected is 80 μm, and density is 0.3g/cm3.
Performance detection is carried out to the material of embodiment 1 shaping, compression strength test a size of 50 × 50 × 50mm, water absorption rate
Sample dimensions are 100 × 100 × 100mm, and experimental condition is hydrostatic pressing 20mpa, pressurize 24h.
The correlated performance of table 2 embodiment 1
As can be seen from Table 2, organic/inorganic tiny balloon according to the present invention compounds and prepares deep water buoyant material density
Relatively low, density is 0.45g/cm3, compressive resistance is 35mpa, can be applied to 2000m with the marine environment of headwater depth, particularly
Under waiting hydrostatic pressing 20mpa, pressurize 24h water absorption rate is less than 1%.This organic/inorganic tiny balloon compounds prepares deep water buoyancy material
Still can carry out sawing after material curing molding, machining and the relevant subsequent working process such as dig, grind, inlaying.And can be selected for multiple soft
Property water-repellent paint carry out surface coating, and the bonding of its base material and finish paint is closely.
Embodiment 2:
Compound according to table 3 proportioning organic/inorganic tiny balloon respectively and prepare deep water buoyant material, concrete preparation method is:
(1) in terms of mass fraction, take 100 parts of unsaturated-resins, 2 parts, 1 part accelerator of curing agent to add in reactor, mix
Close uniformly, obtain resin adhesive liquid；
(2) in terms of mass fraction, 12 parts of organic tiny balloons, 40 parts of inorganic hollow microspheres are taken to add in de-airing mixer,
Mix；
(3) will obtain in the resin adhesive liquid that obtain in above-mentioned steps 1 and step 2 mixing tiny balloon addition vacuum stirring
In machine, vacuum stirring, mixing speed 25r/min, mixing time 40min, mix；
(4) mixed material obtaining in above-mentioned steps 3 is put in vacuum drying chamber, vacuum defoamation under normal temperature；
(5) material obtaining above-mentioned steps 4 is poured in various moulds, by normal temperature cure shaping.
Table 3 ocean deepwater pipeline light heat insulating material parts by weight of component
| Epoxy vingl ester resin | Curing agent | Initiator | Organic tiny balloon | Inorganic hollow microspheres | |
| Embodiment 2 | 100 | 2 | 1 | 12 | 40 |
In table 3: methyl ethyl ketone peroxide selected by curing agent；Accelerator selects cobalt naphthenate or cobalt iso-octoate；Organic hollow
Microballoon is hollow epoxide resin microballoon and/or polyethylene tiny balloon, and the particle diameter of selection is 20 μm, and density is 0.15g/cm3；Institute
Stating inorganic hollow microspheres is hollow glass micro-ball, and the particle diameter that this hollow glass microballoon is selected is 80 μm, and density is 0.3g/cm3.
Performance detection is carried out to the material of embodiment 2 shaping, compression strength test a size of 50 × 50 × 50mm, water absorption rate
Sample dimensions are 100 × 100 × 100mm, and experimental condition is hydrostatic pressing 20mpa, pressurize 24h.
The correlated performance of table 4 embodiment 2
As can be seen from Table 4, organic/inorganic tiny balloon according to the present invention compounds and prepares deep water buoyant material density
Relatively low, density is 0.44g/cm3, compressive resistance is 33mpa, can be applied to 2000m with the marine environment of headwater depth, particularly
Under waiting hydrostatic pressing 20mpa, pressurize 24h water absorption rate is less than 1%.This organic/inorganic tiny balloon compounds prepares deep water buoyancy material
Still can carry out sawing after material curing molding, machining and the relevant subsequent working process such as dig, grind, inlaying.And can be selected for multiple soft
Property water-repellent paint carry out surface coating, and the bonding of its base material and finish paint is closely.
Embodiment 3:
Compound according to table 5 proportioning organic/inorganic tiny balloon respectively and prepare deep water buoyant material, concrete preparation method is:
(1) in terms of mass fraction, take 100 parts of unsaturated-resins, 2 parts, 1 part accelerator of curing agent to add in reactor, mix
Close uniformly, obtain resin adhesive liquid；
(2) in terms of mass fraction, 12 parts of organic tiny balloons, 40 parts of inorganic hollow microspheres are taken to add in de-airing mixer,
Mix；
(3) will obtain in the resin adhesive liquid that obtain in above-mentioned steps 1 and step 2 mixing tiny balloon addition vacuum stirring
In machine, vacuum stirring, mixing speed 25r/min, mixing time 40min, mix；
(4) mixed material obtaining in above-mentioned steps 3 is put in vacuum drying chamber, vacuum defoamation under normal temperature；
(5) material obtaining above-mentioned steps 4 is poured in various moulds, by normal temperature cure shaping.
Table 5 ocean deepwater pipeline light heat insulating material parts by weight of component
| Epoxy vingl ester resin | Curing agent | Initiator | Organic tiny balloon | Inorganic hollow microspheres | |
| Embodiment 3 | 100 | 2 | 1 | 15 | 40 |
In table 5: methyl ethyl ketone peroxide selected by curing agent；Accelerator selects cobalt naphthenate or cobalt iso-octoate；Organic hollow
Microballoon is hollow epoxide resin microballoon and/or polyethylene tiny balloon, and the particle diameter of selection is 20 μm, and density is 0.15g/cm3；Institute
Stating inorganic hollow microspheres is hollow glass micro-ball, and the particle diameter that this hollow glass microballoon is selected is 80 μm, and density is 0.3g/cm3.
Performance detection is carried out to the material of embodiment 3 shaping, compression strength test a size of 50 × 50 × 50mm, water absorption rate
Sample dimensions are 100 × 100 × 100mm, and experimental condition is hydrostatic pressing 20mpa, pressurize 24h.
The correlated performance of table 6 embodiment 3
As can be seen from Table 6, organic/inorganic tiny balloon according to the present invention compounds and prepares deep water buoyant material density
Relatively low, density is 0.41g/cm3, compressive resistance is 30mpa, can be applied to 2000m with the marine environment of headwater depth, particularly
Under waiting hydrostatic pressing 20mpa, pressurize 24h water absorption rate is less than 1%.This organic/inorganic tiny balloon compounds prepares deep water buoyancy material
Still can carry out sawing after material curing molding, machining and the relevant subsequent working process such as dig, grind, inlaying.And can be selected for multiple soft
Property water-repellent paint carry out surface coating, and the bonding of its base material and finish paint is closely.
Organic/inorganic tiny balloon of the present invention compounds prepares deep water buoyant material, wherein organic hollow glass micropearl with no
Machine cenosphere stirring at low speed mixing method.
The content not illustrated in the present embodiment is prior art, therefore is no longer described in detail.
The advantage that organic/inorganic tiny balloon of the present invention compounds the deep water buoyant material of preparation: material prescription is flexibly, permissible
Each amounts of components is adjusted using the depth of water in formula range according to product, reaches the light material mating with using depth；Pass through
There are tiny balloon and inorganic hollow microspheres to compound, significantly reduce the density of buoyant material, there is higher-strength simultaneously；Density
For 0.40 to 0.45g/cm3, compressive resistance 30, to 35mpa, meets the universal material requirements in deep-sea, good quality, and this shaping
Method is relatively low to equipment requirement, and moulding process is simple, low cost.
Unsaturated-resin of the present invention is epoxy vingl ester resin, has that viscosity is low, density is low, high strength after curing
Characteristic.
Organic tiny balloon uniform particle sizes that the present invention uses, compressive resistance are high, high with matrix resin interface binding power.
The inorganic microsphere hollow glass micro-ball uniform particle sizes that the present invention uses, its floatability are higher, pressure functional.
Normal temperature cured type curing agent selected by the curing agent that the present invention uses, can be with the machinery of the organic tiny balloon of effective protection
Performance is it is ensured that buoyant material quality.The accelerator using is cobalt salt class, effectively can control the reaction time, effectively controls
Material mixes.Described organic tiny balloon is hollow epoxide resin microballoon and/or polyethylene tiny balloon, the particle diameter of selection
For 20 μm, density is 0.15g/cm3；Described inorganic hollow microspheres are hollow glass microballoon, and this hollow glass microballoon selects particle diameter
For 80 μm, density is 0.3g/cm3.According to compounding principle, realize closestpacking, increase microballoon amount, reduce system density, protect
Card quality of materials.
The present invention by organic tiny balloon, inorganic hollow microspheres and unsaturated-resin reasonable coordination, combination and according to
The cure process of science is prepared, and it is good that the deep water buoyant material therefore prepared has lightweight, high-strength and compactness
Performance characteristics, and preparation method is simply efficient, is easy to operate.
The above, be only presently preferred embodiments of the present invention, and not the present invention is made with any pro forma restriction, all
It is any simple modification, equivalent variations and modification above example made according to the technical spirit of the present invention, all still fall within
In the range of technical solution of the present invention.
Claims (4)
1. a kind of organic deep water buoyant material being compounded with inorganic hollow microspheres, be is characterized in that: is oxireme by mass fraction
100 parts of base resin, 2 parts of methyl ethyl ketone peroxide, cobalt naphthenate or 1 part of cobalt iso-octoate, particle diameter are 20 μm and density is 0.15g/cm3
Hollow epoxide resin microballoon and/or 10 parts of polyethylene tiny balloon and particle diameter is 80 μm and density is 0.3g/cm3Hollow glass
40 parts of compositions of glass microballoon.
2. organic deep water buoyant material being compounded with inorganic hollow microspheres according to claim 1, be is characterized in that: described sky
Heart glass microsphere hollow be filled with air or be vacuum.
3. a kind of preparation method of organic deep water buoyant material being compounded with inorganic hollow microspheres, be is characterized in that:
(1) in terms of mass fraction, 100 parts of epoxy vingl ester resin, 2 parts of methyl ethyl ketone peroxide, cobalt naphthenate or cobalt iso-octoate 1 are taken
Part, add in reactor, be uniformly mixed with stirring rod, obtain resin adhesive liquid；
(2) in terms of mass fraction, take particle diameter be 20 μm and density be 0.15g/cm3Hollow epoxide resin microballoon and/or polyethylene
10 parts of tiny balloon is 80 μm with particle diameter and density is 0.3g/cm340 parts of addition de-airing mixers of hollow glass microballoon in, mix
Close and uniformly obtain mixing microballoon；
(3) described resin adhesive liquid is added in described mixing microballoon, vacuum stirring, mixing speed 25r/min, mixing time
40min, mixes and obtains mixed material；
(4) described mixed material is put in vacuum drying chamber, normal-temperature vacuum deaeration；
(5) it is poured in mould, normal temperature cure is molded.
4. the preparation method of organic deep water buoyant material compounding with inorganic hollow microspheres according to claim 3, it is special
Levying is: described hollow glass micro-ball hollow be filled with air or be vacuum.
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| CN108912707A (en) * | 2018-07-26 | 2018-11-30 | 江苏增光复合材料科技有限公司 | Fibre enhancement epoxy asphalt pavement material and preparation method thereof |
| CN110628180B (en) * | 2019-09-26 | 2021-01-29 | 海洋化工研究院有限公司 | Solid buoyancy material and preparation method thereof |
| CN115160678A (en) * | 2022-08-19 | 2022-10-11 | 阳光水面光伏科技有限公司 | Polyolefin composite material and preparation method and application thereof |
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| CN101985528A (en) * | 2010-11-19 | 2011-03-16 | 咸宁海威复合材料制品有限公司 | Deep sea pressure-resistant workable buoyancy material and production method thereof |
| CN103131040B (en) * | 2013-02-27 | 2014-09-03 | 昆明理工大学 | Hollow microsphere of polymer having non-permeable surface, and its preparation method |
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| CN103665768B (en) * | 2013-11-26 | 2016-08-17 | 上海复合材料科技有限公司 | The preparation method of High-strength solid buoyancy material |
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