CN103085191B - Deep sea pressure-resistant workable buoyancy material and production method thereof - Google Patents
Deep sea pressure-resistant workable buoyancy material and production method thereof Download PDFInfo
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- CN103085191B CN103085191B CN201310065622.8A CN201310065622A CN103085191B CN 103085191 B CN103085191 B CN 103085191B CN 201310065622 A CN201310065622 A CN 201310065622A CN 103085191 B CN103085191 B CN 103085191B
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Abstract
The invention provides a kind of deep sea pressure-resistant workable buoyancy material, its component comprises procedure of processing: 1) material is stirred in mixing: by described component configuration material, material is added vacuum kneader, stirs; 2) vacuum stirring deaeration: after mix and blend, covers vacuum kneader sealing and vacuumizes, continue to stir material; 3) discharging: the material after vacuum stirring deaeration is proceeded in mould and shapes; 4) demoulding: treat the thorough curing and demolding of material; Wherein 3) material in mould described in step in sizing also comprises vacuum vibration deaeration.This material also has the extremely low characteristic of water absorption rate, can be used for field, 500 ~ 7000 meters of deep-seas and to dive the manufacture of device.By vacuum stirring and vacuum vibration deaeration technology in technique, the air bubble content adopting very not complicated technique just to solve similar material in prior art is difficult to greatly the problem removed.
Description
Technical field
The present invention relates to underwater hiding-machine solid buoyancy material, refer to a kind of deep sea pressure-resistant workable buoyancy material and production method thereof particularly.
Background technology
In recent years, Ocean Technology in China is fast-developing, obtains comparatively much progress in seafari, monitoring etc., and deep water high intensity buoyancy material is own through becoming the important component part developing modern deep diving technology.Low-density, High-strength deepwater solid buoyancy material obtain and apply more and more widely, wherein especially with can processing type buoyant material because of its machinability, have broader application.
High resistance to compression, the low-density buoyant material of development both at home and abroad are at present mainly binding agent with epoxy resin, and a large amount of filling hollow glass micropearl and additive are combined into the lightweight buoyancy material of excellent performance.
It is matrix with epoxy resin that Chinese patent CN200610043524.4 describes a kind of, fill hollow glass micropearl and/or ceramic fine bead, after stirring in kneader, compound is put into mould, compacting, is placed in pressure-cure machine, Pressurized-heated, solidification certain hour obtains material standard module, and such density of material is at 0.5g/cm
3below, withstand voltage 12.5Mpa, density 0.6g/cm
3material can be applied to 5800 meters of deepwater works, its comprehensive comparison is excellent, but its manufacture craft relative complex, after mixing of materials stirs, turns compacting in mould, then is placed in pressure-cure machine Pressurized-heated, bubble is reduced Post RDBMS.
Chinese patent CN200810015375.X describes a kind of preparation method and equipment of polyalcohol-base light overpressure resistant floating force material.In the method, the material of mixing and stirring is proceeded to one special can continue regulate pressure container in, this container comprises metal shell layer, pressure regulating course, crown cap of exerting pressure, fastening screw, positioning screw, separation layer, charging aperture, air outlet slit etc., by giving the pressure that in solidification, material one is lasting, and a reserved air outlet slit, the bubble be mixed in material is gone out beyond material by continuous extrusion.
In above method, material deaeration needs high-temperature and high-pressure conditions, or the mould of Special complex and stripper apparatus, and its technique is all more complicated, and production cost is high, efficiency is lower, is subject to larger restriction.
Chinese patent 101985528A discloses a kind of deep sea pressure-resistant workable buoyancy material and production method thereof, it is 2011-03-16 that Gongwei opens day, to disclose in buoyant material component vinyl ester resin and unsaturated polyester resin one or both, curing agent, promoter, plasticized modifier, dispersant, diluent, coupling agent and cenosphere, production stage is: material-vacuum stirring deaeration-discharging-solidification and the demoulding are stirred in mixing, although reach certain technique effect, in technique, end reaches best.
Summary of the invention
Object of the present invention will provide a kind of deep sea pressure-resistant workable buoyancy material exactly, and this buoyant material has that density is low, compressive resistance is high, water absorption rate is extremely low and have the features such as machinability, can be used for field, 500 ~ 7000 meters of deep-seas and to dive the manufacture of device.
Of the present invention another provides a kind of technique simple, processing method with low cost.
The present invention also provides a kind of vacuum vibration machine for deep sea pressure-resistant workable buoyancy material processing
For achieving the above object, the deep sea pressure-resistant workable buoyancy material designed by the present invention, its component comprises procedure of processing: 1) material is stirred in mixing: by designed parts by weight of component configuration material, material is added vacuum kneader, stirs;
2) vacuum stirring deaeration: after mix and blend, covers vacuum kneader sealing and vacuumizes, continue to stir material;
3) discharging: the material after vacuum stirring deaeration is proceeded in mould and shapes;
4) demoulding: treat the thorough curing and demolding of material;
Wherein 3) material in mould described in step in sizing also comprises vacuum vibration deaeration.
Mould is put into vacuum vibration machine together with material and is carried out vacuum vibration and remove bubble by vacuum vibration deaeration exactly, keeps 1 ~ 3min after vacuum reaches more than 99%.
Component to comprise in vinyl ester resin and unsaturated polyester resin one or both, initator, promoter, dispersant, diluent, coupling agent and cenosphere; Wherein components by weight percent is:
In vinyl ester resin and unsaturated polyester resin one or both 100
Initator 3
Promoter 1
Dispersant 0.5
Diluent 5
Coupling agent 2
Cenosphere 5 ~ 150.
Initator preferred molecular weight 150 ~ 500 organic per-compounds.
The preferred cobalt naphthenate solution of promoter.
Dispersant is preferably the unsaturated polynary carboxylic ester polymer of molecular weight in 300 ~ 2000 scopes and the mixture of organosiloxane copolymer.
Coupling agent preferentially selects γ-glycidoxy trimethoxy silane.
Diluent is preferably styrene.
Cenosphere selects one or more in hollow glass bead, ceramic hollow microballon or polymeric hollow microballon.The size controlling of cenosphere is in 15 ~ 150um scope, and compressive resistance controls in 0.5 ~ 70MPa scope, and bulk density controls at 0.02 ~ 0.5g/cm
3scope.
A processing method for deep sea pressure-resistant workable buoyancy material, comprises step:
1) material is stirred in mixing: by designed parts by weight of component configuration material, material is added vacuum kneader, stirs;
2) vacuum stirring deaeration: after mix and blend, covers vacuum kneader sealing and vacuumizes, continue to stir material;
3) discharging: the material after vacuum stirring deaeration is proceeded in mould and shapes;
4) demoulding: treat the thorough curing and demolding of material;
Wherein 3) material in mould described in step in sizing also comprises vacuum vibration deaeration.
Mould is put into vacuum vibration machine together with material and is carried out vacuum vibration and remove bubble by vacuum vibration deaeration exactly, keeps 1 ~ 3min after vacuum reaches more than 99%.
A kind of vacuum vibration machine for the preparation of deep sea pressure-resistant workable buoyancy material, comprise and form enclosure cavity by metal or other rigid material shell, enclosure cavity is provided with the dodge gate for putting into or take out buoyant material, enclosure cavity has for being connected to straight empty pump and exhaust tube, the display vacuum meter of vacuum and the air intake valve for air inlet for vacuumizing, and inside cavity is provided with the shaking device for shaking buoyant material.Shaking device is electromagnetic shock equipment, and this equipment has the metal plate for placing buoyant material.Dodge gate is hinged through the hinge to enclosure cavity, and dodge gate is provided with the bolt described dodge gate and face, cavity hatch place compressed when closing, and one deck compressible rubber band is posted border at dodge gate place.
In buoyant material production method of the present invention, to limit reason as follows for deaeration mechanism and operating procedure and parameter: have there is bubble in mobility system time, there is surface tension in bubble surface, bubble is caused to be difficult to break, and due to bubble phase much smaller to density ratio matrix, also can be subject to buoyancy, there is frictional force in matrix system and bubble interface simultaneously, when system viscosity more hour, between bubble surface and matrix system, frictional force is less, bubble is easier under buoyancy progressively to rise floating to top layer, so when material bodies viscosity more hour, more be conducive to bubble floating, and top layer bubble connects with air, bubble more easily breaks, and buoyant material should add the hollow beads powder of more parts as far as possible in order to reach lower density, adding of microballon powder, the viscosity of material system can be strengthened, so answer conservative control material system viscosity, density of material can be reduced as far as possible under satisfied elimination bubble requirement condition, through lot of experiments, material system viscosity controls at 10000-20000cps as best.
Under 10000-20000cps viscosity; bubble from ascent rate in material slowly; by adding a certain amount of dispersant; improve material fluidity; can to a certain degree reduce frictional force between bubble and material; gas bubble light soil and bubble discharge can be accelerated, but still bubble cannot be discharged completely.
Under natural atmosphere environment, bubble inner air pressure is an atmospheric pressure, about 0.1MPa, when environmental pressure residing for material reduces, bubble inside by reason of heavy pressure, external and internal pressure there are differences, for keeping balance, then bubble can expand and become large, until reach balance, do not considering under bubble skin surface tension, when environment vacuum degree reaches 99%, bubble external pressure is inner 1%, perfect condition bubble need expand 100 times of large guarantee internal and external pressure balances, and when bubble external pressure is zero, bubble will infinitely expand until break in theory, actual in surface tension existence, bubble can not expand so much times, but when vacuum reaches more than 99%, bubble energy decades of times expands, whole material system is formed as cell foams shape, bubble all connects and communicates and break, bubbles burst can be accelerated further under vibrations or stirring condition, and after bubbles burst under continuation vacuumized conditions, in bubble, air is discharged and takes away, after bubble vacuum stirring or vacuum vibration terminate, in environment residing for material and material, almost there is not air in oneself, when material is returned in atmospheric pressure environment, even if a small amount of granule bubble may be remained in material, due to its under the above condition of 99% vacuum time bubble internal gas pressure value lower than 1% atmospheric pressure, when ambient pressure is returned to atmospheric pressure, bubble internal pressure is far smaller than external pressure, under external pressure effect, bubble will reduce rapidly until inner and outer air pressure keeps balance, namely steep internal gas pressure and also will be returned to atmospheric pressure, needs are reduced more than 100 times by bubble, under vacuum stirring/vibrations exhaust conditions, even if a small amount of residual granule bubble may be there is, and residual granule bubble is reducing after more than 100 times, it is own suitable with hollow beads grain size, bubble size is little, content is few, can ignore oneself warp of material property impact, oneself is through having an impact to material property again.
After mixing of materials, after vacuum stirring deaeration, in material, bubble is own through being eliminated, when the material mixed is proceeded in mould, because material and mould contact surface impregnation process may form air cavity, material proceeds in mould also can be mixed into part bubble, for thoroughly being eliminated by bubble in material, again material is proceeded in vacuum vibration machine together with mould and carry out vacuum vibration deaeration, after solidification and the demoulding, namely obtain buoyant material.
The present invention has the feature of low-density, high strength by adopting the cenosphere standby buoyant material processed of resin-made of filling a vacancy, and facts have proved, this material also has the extremely low characteristic of water absorption rate, can be used for field, 500 ~ 7000 meters of deep-seas and to dive the manufacture of device.By vacuum stirring and vacuum vibration deaeration technology in technique, the air bubble content adopting very not complicated technique just to solve similar material in prior art is difficult to greatly the problem removed.
Accompanying drawing explanation
Fig. 1 is vacuum vibration machine schematic diagram
1 enclosure cavity 2 dodge gate 3 rubber seal tape 4 hinge 5 bolt 6 jarring machine 7 metal plate
8 control to vacuumize and switch 9 intake valve 10 vacuum meter 11 exhaust tube (being connected vavuum pump) shaken
Be further described below in conjunction with accompanying drawing:
Vacuum vibration machine comprises one and vacuumizes the enclosure cavity 1 with the switch 8 shaken with intake valve 9, vacuum meter 10 and control, also comprise with one for put into or take out buoyant material and have the dodge gate 2 of rubber seal tape 3, dodge gate 2 is connected by hinge 4 with enclosure cavity 1, for the bolt 5 at fixed gate at closing time on the cavity of the movable end of dodge gate 2, the metal plate 7 for putting buoyant material also having jarring machine 6 in enclosure cavity 1 and be placed on jarring machine 6.
Detailed description of the invention
Below in conjunction with specific embodiment, buoyant material of the present invention and production method thereof are described in further detail.
Table 1 enumerates nine kinds of different formulations of the present invention or technique buoyant material parts by weight of component when technique.
Table 1 representative formula example formulations table
Note: under above normal temperature selected by table medium vinyl ester resin, viscosity is less than 1000cps low-viscosity type resin; Peroxidized t-butyl perbenzoate selected by initator; Promoter is cobalt naphthenate solution; Dispersant is BYK-906 dispersant; Diluent is styrene; Coupling agent is KH-570 coupling agent; " A " model cenosphere be particle diameter at 10-100um, compression strength 0.5MPa, bulk density is 0.02g/cm
3polymeric hollow microballon; " B " model cenosphere be particle diameter at 30-150um, compression strength 1.7MPa, bulk density is 0.07g/cm
3hollow glass bead; " C " model cenosphere be particle diameter at 15-65um, compression strength 70MPa, bulk density is 0.5g/cm
3ceramic base cenosphere; In deaeration mode project, beat " √ " and represent corresponding deaeration mode technique.
The deep sea pressure-resistant workable buoyancy material of embodiment each in table 1 is produced obtained through following steps:
1) batch mixing and vacuum stirring deaeration: by the parts by weight of component recipe ratio of embodiment each in table 1, resin, cenosphere, curing agent, various additives and auxiliary agent etc. are added after in vacuum kneader, stirs.All be mixed into after in resin matrix until hollow beads powder, material is carried out vacuum stirring, reach after more than 99% until the display of kneader vacuum meter, continue vacuum stirring material 5 ~ 10min.
2) discharging: the material after vacuum stirring deaeration is proceeded in mould;
3) vacuum vibration deaeration: proceed in vacuum vibration machine simultaneously by material and mould, carry out vacuum vibration, reaches after more than 99% until the display of vacuum vibration vacuum meter, continues vacuum vibration 1 ~ 3min.
4) solidification and the demoulding: after vacuum vibration after material nature normal temperature cure or elevated cure, the demoulding i.e. obtained corresponding buoyant material.
Carry out mechanics properties testing to each embodiment product of real table 1, testing result is as table 2.
Table 2 is the mechanical property of each embodiment in table 1:
As can be seen from the above table, buoyant material under equivalent formulation condition, does not adopt deaeration technique, and in buoyant material, bubble is containing larger, than employing vacuum stirring and the little 0.048-0.065g/cm of vacuum vibration associating deaeration density of material
3, lightweight about about 10%, i.e. air bubble content about 10%, material combination property also comparatively declines to a great extent, and water absorption rate is also comparatively large, has a strong impact on material combination property; Make buoyant material density ratio vacuum stirring by vacuum stirring deaeration mode and add the general little 0.006-0.007g/cm of vacuum vibration associating deaeration buoyant material density
3left and right, lightweight about 1%, can be mixed into about 1% bubble when namely material proceeds in mould, material property also has to be affected by a relatively large margin.
The above, formula scheme be only representative instance of the present invention and oneself, be not the restriction done the present invention on formula Design, any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be the Equivalent embodiments of equivalent variations.In every case do not depart from technical solution of the present invention content, any simple modification, equivalent variations and the remodeling done above embodiment according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (2)
1. a deep sea pressure-resistant workable buoyancy material, its buoyant material comprises procedure of processing:
1) material is stirred in mixing: by component configuration material, material is added vacuum kneader, stirs;
2) vacuum stirring deaeration: after mix and blend, covers vacuum kneader sealing and vacuumizes, continue to stir material;
3) discharging: the material after vacuum stirring deaeration is proceeded in mould;
4) demoulding: treat the thorough curing and demolding of material;
It is characterized in that:
Described 3) material in mould described in step in sizing also comprises vacuum vibration deaeration;
Mould is put into vacuum vibration machine together with material and is carried out vacuum vibration and remove bubble by described vacuum vibration deaeration exactly, keeps 1 ~ 3min after vacuum reaches more than 99%;
Described component to comprise in vinyl ester resin and unsaturated polyester resin one or both, initator, promoter, dispersant, diluent, coupling agent and cenosphere; Wherein components by weight percent is:
In vinyl ester resin and unsaturated polyester resin one or both 100
Initator 3
Promoter 1
Dispersant 0.5
Diluent 5
Coupling agent 2
Cenosphere 5 ~ 150
Resin matrix system viscosity should control at below 1000cps, and mixed material viscosity should control at 10000 ~ 20000cps.
2. buoyant material as claimed in claim 1, is characterized in that:
Described initiator molecule amount 150 ~ 500 organic per-compounds;
Described promoter is cobalt naphthenate solution;
Described dispersant is the unsaturated polynary carboxylic ester polymer of molecular weight in 300 ~ 2000 scopes and the mixture of organosiloxane copolymer;
Described coupling agent selects γ-glycidoxy trimethoxy silane;
Described diluent is styrene;
Described cenosphere is one or more in hollow glass bead, ceramic hollow microballon or polymeric hollow microballon; The size controlling of described cenosphere is in 15 ~ 150um scope, and compressive resistance controls in 0.5 ~ 70MPa scope, and bulk density controls at 0.02 ~ 0.5g/cm
3scope.
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| CN104448719B (en) * | 2014-11-13 | 2017-01-25 | 哈尔滨工程大学 | Organic and inorganic hollow microsphere compounded deepwater buoyancy material and preparation method thereof |
| CN110041707B (en) * | 2019-05-14 | 2021-03-19 | 深圳市鼎海新材料技术有限公司 | Flexible pressure-resistant buoyancy material and preparation method thereof |
| CN110570714A (en) * | 2019-09-12 | 2019-12-13 | 上海杉达学院 | high-pressure-resistant deep-sea dummy and manufacturing method thereof |
| CN110698815B (en) * | 2019-10-10 | 2020-10-23 | 海洋化工研究院有限公司 | High-strength solid buoyancy material and preparation method thereof |
| CN113683856B (en) * | 2020-05-18 | 2023-11-28 | 中国科学院理化技术研究所 | Light high-strength solid buoyancy material and preparation method thereof |
| CN113683862B (en) * | 2020-05-18 | 2023-10-31 | 中国科学院理化技术研究所 | Low-density solid buoyancy material suitable for deep sea and preparation method thereof |
| CN114148005A (en) * | 2021-12-27 | 2022-03-08 | 贵州国塑科技管业有限责任公司 | Preparation method of plastic alloy plum blossom pipe |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2734469Y (en) * | 2004-09-02 | 2005-10-19 | 刘建平 | Synthesized stone thin plate extrusion forming machine |
| CN101180166A (en) * | 2005-05-19 | 2008-05-14 | 卢卡·通切利 | Method and plant for manufacturing blocks of conglomerate stone or ceramic material |
| 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 |
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| JPH01261411A (en) * | 1988-04-12 | 1989-10-18 | Nippon Shokubai Kagaku Kogyo Co Ltd | Thermosetting resin composition of low shrinkage |
| CN102408677B (en) * | 2011-09-23 | 2013-03-13 | 江苏省宜兴非金属化工机械厂有限公司 | SiC/epoxy resin composite material and method for manufacturing pump components with it |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2734469Y (en) * | 2004-09-02 | 2005-10-19 | 刘建平 | Synthesized stone thin plate extrusion forming machine |
| CN101180166A (en) * | 2005-05-19 | 2008-05-14 | 卢卡·通切利 | Method and plant for manufacturing blocks of conglomerate stone or ceramic material |
| 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 |
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