CN111909300B - Solid buoyancy material and manufacturing method thereof - Google Patents

Solid buoyancy material and manufacturing method thereof Download PDF

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CN111909300B
CN111909300B CN202010825815.9A CN202010825815A CN111909300B CN 111909300 B CN111909300 B CN 111909300B CN 202010825815 A CN202010825815 A CN 202010825815A CN 111909300 B CN111909300 B CN 111909300B
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hollow glass
mold
glass beads
buoyancy material
solid buoyancy
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CN111909300A (en
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刘刚
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Taizhou Zhongfu New Material Science And Technology Co ltd
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Taizhou Zhongfu New Material Science And Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
    • B29C67/248—Moulding mineral fibres or particles bonded with resin, e.g. for insulating or roofing board
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/28—Glass

Abstract

The invention belongs to the technical field of composite materials, and particularly relates to a solid buoyancy material and a manufacturing method thereof. The solid buoyancy material provided by the invention is prepared from raw materials under the assistance of vacuum; the raw materials comprise the following components in percentage by mass: 55-85% of alkyl styrene; 10-40% of hollow glass beads; 0.5-10% of a cross-linking agent; 0.1-5% of an initiator; 0.01 to 1 percent of accelerant. The solid buoyancy material provided by the invention is prepared from alkyl styrene, an initiator, an accelerant and hollow glass beads under the assistance of vacuum, and experimental results show that: compared with the traditional solid buoyancy material prepared by stirring, mixing and curing epoxy resin and hollow glass beads, the solid buoyancy material provided by the invention has lower density and lower water absorption rate under the same water depth specification.

Description

Solid buoyancy material and manufacturing method thereof
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a solid buoyancy material and a manufacturing method thereof.
Background
The solid buoyancy material is widely applied to deep sea engineering, provides buoyancy for deep water drilling equipment, oil extraction equipment, marine pipe cables, underwater machinery and the like, and is a key component of high-end marine equipment. The solid buoyancy material has a severe working environment, and needs to maintain the working performance and reliability for a long time under the action of very high water pressure, so that the solid buoyancy material is required to have low water absorption and good compressive strength. Meanwhile, the lower density can enable a certain volume of the solid buoyancy material to provide larger net buoyancy, and the solid buoyancy material has higher practical value.
The traditional solid buoyancy material is generally formed by curing and mixing epoxy resin and hollow glass beads after stirring and mixing, and because the epoxy resin has high viscosity and the hollow glass beads are brittle, the hollow glass beads are often damaged in the stirring process, so that the stirred material has high density and high viscosity, and the prepared finished product has unsatisfactory working performance (such as high water absorption) and unstable quality.
Disclosure of Invention
In view of the above, the present invention provides a solid buoyant material and a method for manufacturing the same, and the solid buoyant material provided by the present invention has low density, low water absorption, and high reliability.
The invention provides a solid buoyancy material which is prepared from raw materials under the assistance of vacuum; the raw materials comprise the following components in percentage by mass:
Figure BDA0002636171300000011
preferably, the alkylstyrene comprises t-butylstyrene and/or methylstyrene.
Preferably, the D50 particle size of the hollow glass bead is 5-200 μm; the true density of the hollow glass beads is 50-800 kg/m 3 。
Preferably, the crosslinking agent comprises trimethylolpropane trimethacrylate.
Preferably, the initiator comprises methyl ethyl ketone peroxide and/or benzoyl peroxide.
Preferably, the promoter comprises cobalt naphthenate and/or dimethylaniline.
The invention provides a manufacturing method of the solid buoyancy material in the technical scheme, which comprises the following steps:
filling hollow glass beads into a mold, adding a mixed feed liquid containing alkyl styrene, a cross-linking agent, an initiator and an accelerator into the mold from the upper part of the hollow glass beads, vacuumizing the bottom of the mold to enable the mixed feed liquid to uniformly penetrate into and fill gaps among the hollow glass beads under the combined action of gravity and atmospheric pressure, and finally heating and curing to obtain the solid buoyancy material.
Preferably, before the mixed feed liquid is added, the mold is vibrated to fill the hollow glass beads in the mold.
Preferably, during the evacuation of the bottom of the mold, a compressed gas is injected into the mold from the top of the mold.
Preferably, the heating and curing temperature is 50-120 ℃; the heating and curing time is 0.5-24 h.
Compared with the prior art, the invention provides a solid buoyancy material and a manufacturing method thereof. The solid buoyancy material provided by the invention is prepared from raw materials under the assistance of vacuum; the raw materials comprise the following components in percentage by mass: 55-85% of alkyl styrene; 10-40% of hollow glass beads; 0.5-10% of a cross-linking agent; 0.1-5% of an initiator; 0.01 to 1 percent of accelerant. The solid buoyancy material provided by the invention is prepared from alkyl styrene, an initiator, an accelerant and hollow glass beads under the assistance of vacuum. The alkylstyrene has a lower density than the epoxy resin and can produce a lower density solid buoyant material. And the alkyl styrene has extremely low viscosity and good wettability, so the method is suitable for the production process of vacuum-assisted infiltration. The solid buoyancy material prepared by adopting the vacuum auxiliary infiltration mode avoids the damage of the hollow glass microspheres because the liquid material and the hollow glass microspheres do not need to be stirred, and the filling rate of the hollow glass microspheres in finished products is higher. In addition, in the manufacturing method provided by the invention, the liquid material infiltrates the hollow glass beads filled in the mould from top to bottom, the combined action of the gravity of the liquid material and the air pressure difference under the assistance of vacuum is fully utilized, and the infiltration efficiency is higher; meanwhile, the hollow glass beads are uniformly stressed in the permeation process, and the hollow glass beads cannot be pushed away due to concentrated stress, so that the tight packing of the hollow glass beads is damaged; the situation that the local penetration is too fast and other parts are not penetrated can not occur, so the quality of the product is better and more stable. Experimental results show that compared with the traditional solid buoyancy material prepared by stirring, mixing and curing epoxy resin and hollow glass beads, the solid buoyancy material provided by the invention has lower density and lower water absorption under the same water depth specification.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a schematic view of an evacuation process in an open mold provided by an embodiment of the present invention;
fig. 2 is a schematic diagram of the evacuation process performed in the capping mold according to the embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a solid buoyancy material which is prepared from raw materials under the assistance of vacuum; the raw materials comprise the following components in percentage by mass:
Figure BDA0002636171300000031
the solid buoyancy material provided by the invention is prepared from raw materials under the assistance of vacuum, wherein the raw materials comprise alkyl styrene, hollow glass beads, a cross-linking agent, an initiator and an accelerator. Wherein the alkylstyrene preferably comprises tert-butylstyrene and/or methylstyrene; the content of the alkylstyrene in the raw material is 55 to 85 wt%, specifically 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt%, 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt% or 85 wt%.
In the solid buoyancy material provided by the invention, the D50 particle size of the hollow glass beads is preferably 5-200 μm, and specifically can be 5 μm, 10 μm, 15 μm, 20 μm, 22 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 120 μm, 150 μm, 170 μm or 200 μm; the preferred true density of the hollow glass beads is 50-800 kg/m 3 Specifically, it may be 50kg/m 3 、75kg/m 3 、100kg/m 3 、125kg/m 3 、150kg/m 3 、200kg/m 3 、250kg/m 3 、300kg/m 3 、350kg/m 3 、380kg/m 3 、400kg/m 3 、420kg/m 3 、450kg/m 3 、500kg/m 3 、550kg/m 3 、600kg/m 3 、650kg/m 3 、700kg/m 3 、750kg/m 3 Or 800kg/m 3 (ii) a The isostatic strength of the hollow glass beads is preferably 1-250 MPa, and specifically can be 1MPa, 1.5MPa, 1.7MPa, 2MPa, 5MPa, 10MPa, 15MPa, 20MPa, 30MPa, 38MPa, 40MPa, 50MPa, 55MPa, 60MPa, 80MPa, 100MPa, 120MPa, 140MPa, 160MPa, 180MPa, 200MPa, 230MPa or 250 MPa; the content of the hollow glass beads in the raw material is 10 to 40 wt%, specifically 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt% or 40 wt%.
In the solid buoyancy material provided by the present invention, the cross-linking agent preferably comprises trimethylolpropane trimethacrylate; the content of the crosslinking agent in the raw material is 0.5 to 10 wt%, specifically 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, or 10 wt%.
In the solid buoyancy material provided by the invention, the initiator preferably comprises methyl ethyl ketone peroxide and/or benzoyl peroxide; the content of the initiator in the raw material is 0.1 to 5 wt%, specifically 0.1 wt%, 0.2 wt%, 0.5 wt%, 0.7 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 1.7 wt%, 2 wt%, 2.3 wt%, 2.5 wt%, 2.7 wt%, 3 wt%, 3.2 wt%, 3.5 wt%, 3.7 wt%, 4 wt%, 4.2 wt%, 4.5 wt%, 4.7 wt%, or 5 wt%.
In the solid buoyant material provided by the present invention, the accelerant preferably comprises cobalt naphthenate and/or dimethylaniline; the content of the accelerator in the raw material is 0.01 to 1 wt%, specifically 0.01 wt%, 0.02 wt%, 0.05 wt%, 0.07 wt%, 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.35 wt%, 0.4 wt%, 0.45 wt%, 0.5 wt%, 0.55 wt%, 0.6 wt%, 0.65 wt%, 0.7 wt%, 0.75 wt%, 0.8 wt%, 0.85 wt%, 0.9 wt%, 0.95 wt%, or 1 wt%.
The invention also provides a manufacturing method of the solid buoyancy material in the technical scheme, which comprises the following steps:
filling hollow glass beads into a mold, adding a mixed feed liquid containing alkyl styrene, a cross-linking agent, an initiator and an accelerator into the mold from the upper part of the hollow glass beads, vacuumizing the bottom of the mold to enable the mixed feed liquid to uniformly penetrate into and fill gaps among the hollow glass beads under the combined action of gravity and atmospheric pressure, and finally heating and curing to obtain the solid buoyancy material.
In the manufacturing method provided by the present invention, hollow glass beads are first filled into a mold. Wherein, the bottom of the mould is provided with a through hole for vacuumizing, and the through hole is connected with a valve; the bottom surface of the mould is paved with a screen, and the mesh size of the screen is smaller than the diameter of the hollow glass beads and is used for preventing the hollow glass beads from leaking from the through holes at the bottom of the mould. In the present invention, to facilitate the release of the article, the inner surface of the mold is preferably coated with a release agent.
In the manufacturing method provided by the invention, after the hollow glass beads are filled, mixed feed liquid containing alkyl styrene, a cross-linking agent, an initiator and an accelerator is added into the die from the upper part of the hollow glass beads. In the invention, before the mixed feed liquid is added, the mould is preferably vibrated, so that the hollow glass beads are filled in the mould; the frequency of the vibration is preferably 0.1-20 Hz, and specifically can be 0.1Hz, 0.5Hz, 1Hz, 2Hz, 3Hz, 4Hz, 5Hz, 6Hz, 7Hz, 8Hz, 9Hz, 10Hz, 11Hz, 12Hz, 13Hz, 14Hz, 15Hz, 16Hz, 17Hz, 18Hz, 19Hz or 20 Hz; the vibration time is preferably 5min to 24h, and specifically may be 5min, 10min, 15min, 20min, 25min, 30min, 40min, 50min, 60min, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 14h, 16h, 18h, 20h, 22h or 24 h. In the invention, the mixed feed liquid is prepared by mixing alkyl styrene, a cross-linking agent, an initiator and an accelerator; the mixing process is preferably to mix the alkylstyrene, the cross-linking agent and the initiator uniformly, and then mix the mixture with the accelerator.
In the manufacturing method provided by the invention, after the mixed feed liquid is added, the bottom of the mold is vacuumized, as shown in fig. 1. Fig. 1 is a schematic view of a vacuum process performed in an open mold according to an embodiment of the present invention, in fig. 1, 1 indicates a mold, 2 indicates porous glass beads, 3 indicates a mixed feed liquid, 4 indicates a screen, and 5 indicates a valve connected to a through hole at the bottom of the mold. In the invention, in the process of vacuumizing, the mixed feed liquid permeates into and fills gaps among the hollow glass beads under the action of air pressure; the vacuum degree of the vacuumizing is preferably more than or equal to 0.09 MPa. In the present invention, in order to allow the mixed liquid to penetrate into the gaps between the hollow glass beads more quickly and efficiently, it is preferable to inject a compressed gas into the mold from the top of the mold during the evacuation process, as shown in fig. 2. Fig. 2 is a schematic view of the evacuation process in a capped mold according to an embodiment of the present invention, in fig. 1, 1 indicates a mold, 2 indicates porous glass beads, 3 indicates a mixed feed liquid, 4 indicates a mesh, 5 indicates a valve attached to a through hole at the bottom of the mold, 6 indicates a cap, and 7 indicates a valve attached to a through hole of the cap. In the invention, the compressed gas is preferably compressed air, and the injection pressure of the compressed gas is preferably more than or equal to 1 MPa. In the invention, the infiltration and filling conditions of the mixed feed liquid to the gaps of the hollow glass beads can be judged according to whether the mixed feed liquid flows out of the through holes at the bottom of the die; when the mixed liquid is about to flow out from the through hole at the bottom, the mixed liquid is considered to be completely infiltrated and filled in the gap of the hollow glass microsphere.
In the manufacturing method provided by the invention, after the mixed liquid material is completely soaked and filled in the gaps of the hollow glass microspheres, the vacuum source (and the compressed air source) is removed, and then the mold is heated to solidify the material filled in the mold. Wherein the heating device is preferably an oven; the curing temperature is preferably 50-120 ℃, and specifically can be 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃; the curing time is preferably 0.5-24 h, and specifically can be 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24 h. And after solidification, removing the solidified material from the mold to obtain the solid buoyancy material provided by the invention.
The solid buoyancy material provided by the invention is prepared from alkyl styrene, an initiator, an accelerant and hollow glass beads under the assistance of vacuum. The alkylstyrene has a lower density than the epoxy resin and can produce a lower density solid buoyant material. And the alkyl styrene has extremely low viscosity and good wettability, so the method is suitable for the production process of vacuum-assisted infiltration. The solid buoyancy material prepared by adopting the vacuum auxiliary infiltration mode avoids the damage of the hollow glass microspheres because the liquid material and the hollow glass microspheres do not need to be stirred, and the filling rate of the hollow glass microspheres in finished products is higher. In addition, in the manufacturing method provided by the invention, the liquid material infiltrates the hollow glass beads filled in the mould from top to bottom, the combined action of the gravity of the liquid material and the air pressure difference under the assistance of vacuum is fully utilized, and the infiltration efficiency is higher; meanwhile, the hollow glass beads are uniformly stressed in the permeation process, so that the hollow glass beads are not pushed away due to concentrated stress, and the tight packing of the hollow glass beads is damaged; the situation that the local penetration is too fast and other parts are not penetrated can not occur, so the quality of the product is better and more stable. Experimental results show that compared with the traditional solid buoyancy material prepared by stirring, mixing and curing epoxy resin and hollow glass beads, the solid buoyancy material provided by the invention has lower density and lower water absorption under the same water depth specification.
For the sake of clarity, the following examples are given in detail.
Example 1
1) Preparing an open steel mould with the internal dimensions of 400mm wide, 500mm long and 300mm high, a through hole at the bottom and a valve connected on the through hole; uniformly coating a release agent on all inner surfaces of the mould; and a screen with the width of 400mm, the length of 500mm and the mesh number of 300 is paved on the bottom surface of the screen.
2) 2kg of a medium diameter (D50) of 65 μm and a true density of 125kg/m were poured into the mould 3 Hollow glass microspheres with compressive strength of 1.7 MPa; the mold was placed on a vibration table and vibrated at a frequency of 10Hz for 15 minutes.
3) 12kg of t-butylstyrene, 0.5kg of trimethylolpropane trimethacrylate and 0.25kg of methyl ethyl ketone peroxide were uniformly stirred to prepare a mixed solution 1.
4) And uniformly stirring the mixed solution 1 and 0.05kg of cobalt naphthenate to prepare a mixed solution 2.
5) Pouring the mixed solution 2 into a mould, connecting a vacuum source to a through hole at the bottom of the mould, opening a valve, and vacuumizing until the vacuum degree is more than 0.09 MPa.
6) Waiting for the mixed solution 2 to completely infiltrate the filled hollow glass microspheres and fill the gaps of the hollow glass microspheres under the action of atmospheric pressure and vacuum pressure difference; the specific situation can be observed through the opening of the mold, and whether the through hole at the bottom of the mold has liquid material flowing out is judged, and the process lasts for about 90 minutes.
7) Removing the vacuum source and closing the mold bottom valve; and the mold was placed in an oven and cured at 100 ℃ for 2 hours.
8) And (4) releasing the cured finished product from the mold to obtain the novel solid buoyancy material 1.
The density of the solid buoyancy material 1 was tested to be 320kg/m 3 The compressive strength is 8MPa, and the water absorption rate is 0.3 percent under the hydrostatic pressure of 5MPa for 24 hours; the compressive strength of the material is not less than 1.25 times of the water depth pressure (5MPa) of 500m, and the water absorption rate under the hydrostatic pressure of 5MPa is less than 1.0 percent, so the material is suitable for the solid buoyancy material under the water depth of 500 m.
Example 2
1) Preparing an aluminum mould with the internal dimensions of 800mm wide, 1200mm long and 600mm high, a through hole at the bottom and a valve connected on the through hole; uniformly coating a release agent on all the inner surfaces of the mould; and a screen mesh with the width of 800mm, the length of 1200mm and the mesh number of 1000 is laid on the bottom surface of the screen mesh.
2) A cover is prepared for airtight connection with the mold, and has a through hole at its top, and a valve is connected to the through hole.
3) 80kg of a medium diameter (D50) of 40 μm and a true density of 380kg/m were poured into the mould 3 Hollow glass beads with compressive strength of 38 MPa; the mold was placed on a vibrating platform and vibrated at a frequency of 0.5Hz for 480 minutes.
4) 155kg of methylstyrene, 2kg of trimethylolpropane trimethacrylate and 1.6kg of benzoyl peroxide are stirred uniformly to obtain a mixed solution 3.
5) And uniformly stirring the mixed solution 3 and 0.2kg of dimethylaniline to prepare a mixed solution 4.
6) Pouring the mixed solution 4 into a mould, and firmly connecting the cover with the mould.
7) Connecting a vacuum source to a through hole at the bottom of the mold, opening a valve, and vacuumizing until the vacuum degree is more than 0.09 MPa; meanwhile, a compressed air source is connected with a through hole at the top of the cover, a valve is opened, and the air is added to the pressure of 1 MPa.
8) Waiting for the mixed liquid 4 to completely infiltrate the filled hollow glass microspheres and fill the gaps of the hollow glass microspheres under the action of the pressure difference between the compressed air and the vacuum; the process can be judged according to whether liquid material flows out of the through hole at the bottom of the die or not, and lasts for about 20 minutes.
9) Removing the vacuum source and closing the mold bottom valve; removing the compressed air source and closing the lid top valve; the mold was placed in an oven and cured at 60 ℃ for 24 hours.
10) And (4) releasing the cured finished product from the mold to obtain the novel solid buoyancy material 2.
The density of the solid buoyant material 2 was tested to be 540kg/m 3 The compressive strength is 85MPa, and the water absorption rate is 0.1% under the hydrostatic pressure of 60MPa for 24 hours; the compressive strength of the material is not less than 1.25 times of the 6000m water depth pressure (60MPa), and the water absorption rate under the 60MPa hydrostatic pressure is less than 1.0%, so the material is suitable for the 6000m water depth solid buoyancy material.
Example 3
1) Preparing an open hemispherical steel mould with the inner diameter of 800mm and the bottom provided with a through hole, wherein a valve is connected to the through hole; all the inner surfaces are evenly coated with release agent, and a screen mesh with 2000 meshes which is attached to the hemispherical inner surface is laid.
2) 38kg of a 22 micron diameter median (D50) and a true density of 420kg/m were poured into the mould 3 Hollow glass microspheres with the compressive strength of 55 MPa; the mold was placed on a vibration table and vibrated at a frequency of 3Hz for 60 minutes.
3) 50kg of methyl styrene, 1kg of trimethylolpropane trimethacrylate and 0.5kg of benzoyl peroxide are uniformly stirred to prepare a mixed solution 5.
4) And uniformly stirring the mixed solution 5 and 0.05kg of dimethylaniline to prepare a mixed solution 6.
5) Pouring the mixed solution 6 into a mould, connecting a vacuum source to a through hole at the bottom of the mould, opening a valve, and vacuumizing until the vacuum degree is more than 0.09 MPa.
6) Waiting for the mixed liquid 6 to completely infiltrate the filled hollow glass microspheres and fill the gaps of the hollow glass microspheres under the action of the pressure difference between the atmospheric pressure and the vacuum; the specific situation can be observed through the opening of the mold, and whether liquid material flows out of the through hole at the bottom of the mold is judged; the process lasts approximately 120 minutes.
7) Removing the vacuum source and closing the mold bottom valve; and the mold was placed in an oven and cured at 120 ℃ for 16 hours.
8) And (4) releasing the cured finished product from the mold to obtain the novel solid buoyancy material 3.
The density of the solid buoyant material 3 was tested to be 630kg/m 3 The compressive strength is 100MPa, and the water absorption rate is 0.6 percent under the hydrostatic pressure of 80MPa for 24 hours; the compressive strength of the material is not less than 1.25 times of the water depth pressure (80MPa) of 8000m, and the water absorption rate under the hydrostatic pressure of 60MPa is less than 1.0 percent, so the material is suitable for the solid buoyancy material under the water depth of 8000 m.
Comparative example 1
1) According to the same mass ratio of the hollow glass microspheres and the liquid components as in example 1, the hollow glass microspheres, the bisphenol A epoxy resin and the triethylene tetramine curing agent with the same specification are uniformly stirred in a stirrer according to a traditional manufacturing method, and the mass ratio of the bisphenol A epoxy resin to the triethylene tetramine is 7:1, so that a mixed solution 7 is obtained.
2) The mixed solution 7 was introduced into a mold having the same inner dimensions as those of the mold described in example 1, and the mold was placed in an oven and cured at 50 ℃ for 1 hour.
3) The cured final product was ejected from the mold to yield comparative solid buoyancy material 1.
The density of the comparative solid buoyancy material 1 was tested to be 500kg/m 3 The water absorption rate was 0.5% at hydrostatic pressure of 5MPa for 24 hours.
Comparative example 2
1) According to the same mass ratio of the hollow glass microspheres and the liquid components as in the example 2, the hollow glass microspheres, the bisphenol A epoxy resin, the methyl tetrahydrophthalic anhydride curing agent and the DMP-30 accelerator with the same specification are uniformly stirred in a stirrer according to the traditional manufacturing method, and the mass ratio of the bisphenol A epoxy resin to the methyl tetrahydrophthalic anhydride to the DMP-30 is 100:90:1, so that a mixed solution 8 is obtained.
2) The mixed solution 8 was introduced into a mold having the same inner dimensions as those of the mold described in example 2, and the mold was placed in an oven and cured at 120 ℃ for 6 hours.
3) The cured final product was ejected from the mold to yield comparative solid buoyancy material 2.
The density of the comparative solid buoyancy material 2 was tested to be 650kg/m 3 The water absorption rate was 0.9% at 60MPa hydrostatic pressure for 24 hours.
Comparative example 3
1) According to the same mass ratio of the hollow glass microspheres to the liquid components as in example 3, the hollow glass microspheres, the bisphenol A epoxy resin, the alkyl glycidyl ether diluent and the polyamide curing agent with the same specification are uniformly stirred in a stirrer according to a traditional manufacturing method, and the mass ratio of the bisphenol A epoxy resin to the alkyl glycidyl ether to the polyamide is 100:10:30, so that a mixed solution 9 is obtained.
2) The mixed solution 9 was introduced into a mold having the same inner dimensions as those of the mold described in example 3, and the mold was put into an oven and cured at 100 ℃ for 2 hours.
3) The cured final product was ejected from the mold to yield comparative solid buoyancy material 3.
The density of the comparative solid buoyancy material 3 was tested to be 780kg/m 3 The water absorption rate was 1.3% at 80MPa hydrostatic pressure for 24 hours.
In summary, the performance of the novel solid buoyancy material prepared using the vacuum assisted infiltration method compared to the solid buoyancy material prepared using the conventional agitation method is shown in the following table:
working depth (m) Density (kg/m) 3 ) Water absorption (%)
Example 1 500 320 0.3
Comparative example 1 500 500 0.7
Example 2 6000 540 0.1
Comparative example 2 6000 650 0.9
Example 3 8000 630 0.6
Comparative example 3 8000 780 1.3
The comparison shows that the novel solid buoyancy material prepared by the vacuum-assisted infiltration method has the beneficial effects of lower density and lower water absorption rate under the same water depth specification.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. A method of making a solid buoyant material comprising the steps of:
filling hollow glass beads into a mold, adding a mixed feed liquid containing alkyl styrene, a cross-linking agent, an initiator and an accelerator into the mold from above the hollow glass beads, vacuumizing the bottom of the mold to enable the mixed feed liquid to uniformly penetrate into and fill gaps among the hollow glass beads under the combined action of gravity and atmospheric pressure, and finally heating and curing to obtain a solid buoyancy material;
the solid buoyancy material comprises the following raw materials in percentage by mass:
Figure FDA0003739497920000011
2. the production method according to claim 1, wherein the alkylstyrene comprises t-butylstyrene and/or methylstyrene.
3. The production method according to claim 1, wherein the D50 particle size of the hollow glass bead is 5 to 200 μm; the true density of the hollow glass beads is 50-800 kg/m 3 。
4. The method of manufacturing according to claim 1, wherein the crosslinking agent comprises trimethylolpropane trimethacrylate.
5. The method of manufacturing according to claim 1, wherein the initiator comprises methyl ethyl ketone peroxide and/or benzoyl peroxide.
6. The method of claim 1, wherein the accelerator comprises cobalt naphthenate and/or dimethylaniline.
7. The manufacturing method according to claim 1, wherein the hollow glass microspheres are filled in the mold by vibrating the mold before the mixed material liquid is added.
8. The method of claim 1, wherein the compressed gas is injected into the mold from the top of the mold during the evacuation of the bottom of the mold.
9. The manufacturing method according to claim 1, wherein the temperature for heat curing is 50 to 120 ℃; the heating and curing time is 0.5-24 h.
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CN101735566B (en) * 2009-12-05 2011-08-10 海洋化工研究院 Processable full sea-depth buoyancy material and manufacture method
CN102702679B (en) * 2012-05-31 2015-03-25 中国海洋大学 Preparation method for high-strength solid buoyancy material for deep submergence
CN103483774A (en) * 2013-09-24 2014-01-01 滕州市华海新型保温材料有限公司 High-performance solid buoyancy material and preparation method thereof
CN105424492A (en) * 2015-12-30 2016-03-23 中国建材国际工程集团有限公司 Measuring method for water-resistant isostatic pressure strength of hollow glass microspheres
CN106832789A (en) * 2017-03-21 2017-06-13 钟东南 A kind of integrated molding solid buoyancy material and preparation method thereof
CN107383665B (en) * 2017-08-15 2020-03-24 株洲时代新材料科技股份有限公司 Low-water-rate solid buoyancy material and preparation method thereof
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