CN114644809A - Composition of buoyancy material, buoyancy material and manufacturing method thereof - Google Patents
Composition of buoyancy material, buoyancy material and manufacturing method thereof Download PDFInfo
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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
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
- C08K9/02—Ingredients treated with inorganic substances
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
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- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The invention discloses a composition of a buoyancy material, the buoyancy material and a manufacturing method thereof. The composition of the buoyancy material comprises a thermosetting resin, a plurality of micron-sized hollow spheres, a plurality of nano-sized metal oxide particles and a curing agent. The buoyancy material prepared by the manufacturing method has low water absorption rate through the roughened surface of the hollow spheres and the metal oxide particles.
Description
Technical Field
The present invention relates to a composition of a buoyant material, and a method for manufacturing the same, and more particularly, to a buoyant material with low water absorption, a composition thereof, and a method for manufacturing the same.
Background
Buoyant materials are widely used in civilian, commercial and military applications. For example, the weight of the underwater equipment, the floating cable floating on the water surface or in the water, the buoy, the submarine cable burying machine, the zero-buoyancy support body, the life saving device, the submarine detection device, the unmanned remote-control submersible vehicle and the like. In addition, with the development of marine technology, high strength buoyancy materials play an important role in Unmanned Underwater Vehicles (UUVs), which mainly include Remote Operated Vehicles (ROVs) requiring user operation and Autonomous Underwater Vehicles (AUVs) requiring no user operation.
When the buoyant material is used in the aforementioned applications, the buoyant material must have a low density (e.g., 0.3 g/cm)3To 0.8g/cm3) To stably float in the water, thereby providing buoyancy and ensuring the equilibrium state of the equipment loaded by the buoyancy. Furthermore, the buoyancy material must also have high pressure resistance (e.g., uniaxial compressive strength greater than 5.5MPa) to resist high temperature solarization and seawater erosion. Furthermore, the buoyancy material should have low water absorption (e.g. not more than 1%) to avoid the problems of buoyancy variation and material creep after the material absorbs water.
The present composition of buoyancy material is to mix the small size hollow glass spheres into the epoxy resin as light filler and to make the buoyancy material, such as buoyancy module. The prepared buoyancy material has higher compressive strength, so the buoyancy material has longer service life. However, when the hollow glass beads are mixed with the epoxy resin, the hollow glass beads tend to increase the viscosity of the epoxy resin, and the amount of the hollow glass beads used is limited. Although this problem can be solved by adding a reactive diluent, the reactive diluent causes embrittlement of the cured resin and reduces its mechanical properties. In addition, the curing agent used will reduce the working time of the buoyancy material composition, reducing its workability.
On the other hand, when the composition of the buoyant material is cured, it is necessary to use an environment with extremely low water absorption. However, during the preparation, free water easily enters the embedded gap between heterogeneous composite components (such as hollow glass spheres and epoxy resin) and increases the water absorption rate of the buoyancy material, thereby shortening the service life thereof.
In view of the above, there is a need to develop a new composition of buoyancy material, buoyancy material and method for manufacturing the same, so as to improve the above disadvantages of the conventional buoyancy material and method for manufacturing the same.
Disclosure of Invention
In view of the above problems, it is an object of the present invention to provide a composition of buoyant materials. The prepared buoyancy material has low water absorption rate through the micron-sized hollow spheres and the nanometer-sized metal oxide particles subjected to surface roughening.
Another object of the present invention is to provide a method for manufacturing a buoyant material. The method of making utilizes the composition described above to make a buoyant material, wherein surface roughening of the hollow spheres reduces the water absorption of the buoyant material.
It is another object of the present invention to provide a buoyant material, which is made by the above-mentioned method.
According to one aspect of the present invention, a composition of buoyant materials is provided. The composition comprises a thermosetting resin, a plurality of hollow spheres, a plurality of metal oxide particles and a curing agent, wherein the average particle diameter (D) of the hollow spheres50) Is 10 μm to 100 μm, and the average particle diameter of these metal oxide particles is 5nm to 35 nm. The hollow spheres are used in an amount of 20 to 65 parts by weight, the metal oxide particles are used in an amount of 0.5 to 4.0 parts by weight, and the curing agent is used in an amount of 40 to 60 parts by weight, based on 100 parts by weight of the thermosetting resin.
According to an embodiment of the present invention, the thermosetting resin comprises epoxy resin, phenolic resin, unsaturated polyester resin, and any combination thereof.
According to another embodiment of the present invention, the hollow spheres have a compressive strength of greater than 3000 psi.
According to a further embodiment of the invention, the wall thickness of the hollow spheres is 0.5 μm to 2.5 μm.
According to another object of the invention, a method of manufacturing a buoyant material is provided. The manufacturing method comprises a surface roughening step of roughening a plurality of hollow spheres having an average particle diameter (D)50) Is 10 μm to 100 μm. Next, the modified hollow spheres, the thermosetting resin, and a plurality of metal oxide particles are mixed to obtain a homogenized mixture, wherein the average particle size of the metal oxide particles is 5nm to 35 nm. Then, a curing agent is added to the homogenized mixture for curingAnd (4) carrying out a reaction step to obtain the buoyancy material.
According to one embodiment of the present invention, the surface roughening step comprises washing the hollow spheres with an alkaline solution.
According to another embodiment of the present invention, the surface modification step comprises modifying the hollow spheres with a silane coupling agent.
According to another object of the invention, a buoyant material is provided. The buoyancy material comprises a thermosetting resin, a plurality of hollow spheres and a plurality of metal oxide particles. Average particle diameter (D) of these hollow spheres50) 10 to 100 μm, at least a portion of the metal oxide particles being filled between the hollow spheres, wherein the metal oxide particles have an average particle size of 5 to 35nm, and the water absorption of the buoyant material is no greater than 1%.
According to another embodiment of the present invention, the buoyancy material optionally includes a silane coupling agent bonded to the hollow spheres and/or a silane coupling agent bonded to the metal oxide particles.
According to yet another embodiment of the present invention, the hollow spheres have a compressive strength greater than 3000 psi.
The composition of the buoyancy material and the manufacturing method thereof can increase the wettability of the bonding interface between the composition and the thermosetting resin by the micron-sized hollow spheres with roughened surfaces, and the nano-sized metal oxide particles can be filled in the gaps between the thermosetting resin and the hollow spheres to reduce the water absorption of the buoyancy material, so that the prepared buoyancy material has low water absorption and keeps low density and high compressive strength.
Drawings
For a more complete understanding of the embodiments of the present invention and the advantages thereof, reference is now made to the following descriptions taken in conjunction with the accompanying drawings. It must be emphasized that the various features are not drawn to scale and are for illustrative purposes only. The content of the related figures is explained as follows:
FIG. 1 is a flow chart illustrating a method of manufacturing a buoyant material according to one embodiment of the present invention.
Fig. 2 is a scanning electron micrograph of a buoyant material according to an embodiment of the present invention.
Description of the main reference numerals:
100-method; 110,120,130, 140-operation.
Detailed Description
The making and using of embodiments of the present invention are discussed in detail below. It should be appreciated, however, that the embodiments provide many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed are merely illustrative and do not limit the scope of the invention.
Referring to fig. 1, a flow chart of a method for manufacturing a buoyant material according to an embodiment of the invention is shown. The method 100 first performs a surface roughening step on the hollow spheres, as shown in operation 110. The surface roughening step can roughen the surface of the hollow sphere by using alkali liquor, so that the surface energy of the surface of the hollow sphere is increased, and the subsequent surface modification is facilitated.
In some embodiments, the surface roughening step comprises alkali washing the surface of the hollow sphere with an alkali solution. In other embodiments, the surface roughening step optionally comprises using an ultrasonic wave or electromagnetic wave to facilitate the alkali cleaning, so as to promote the roughening of the hollow sphere surface and greatly increase the surface energy thereof. In other words, in some embodiments, the alkali fluid can clean the surface of the hollow spheres of impurities and/or oil. In some embodiments, the alkaline solution comprises a hydroxide of an alkali metal, and specific examples thereof may include, but are not limited to, lithium hydroxide, sodium hydroxide, and potassium hydroxide, and preferably may be sodium hydroxide.
Further, in some embodiments, the alkali solution is used in an amount of 500 to 800 parts by weight, and the concentration of the alkali solution may be 1 to 3 weight percent, based on 100 parts by weight of the glass microspheres.
In some embodiments, the material of the hollow sphere includes inorganic material and organic material. Specific examples of the hollow spheres may be, but are not limited to, hollow glass spheres, hollow ceramic spheres, and hollow plastic spheres, and preferably may be hollow glass spheres.
In some embodiments, the hollow spheres have an average particle size (D)50) Is 10 μm to 100 μm, and preferably 15 μm to 30 μm. Average particle diameter of hollow sphere (D)50) If the volume is not within the above range, although the smaller hollow ball can increase the compressive strength of the buoyancy material, the too small or too large hollow volume will increase the difficulty of adjusting the density of the buoyancy material, and thus it is difficult to meet the requirement of low density (for example: 0.3g/cm3To 0.8g/cm3). And the hollow sphere with large particle size has relatively poor compression strength, so that the buoyancy material has poor deep pressure resistance.
In some embodiments, the hollow spheres have a compressive strength greater than 3000psi, and preferably greater than 3000psi and no greater than 16000 psi. When the compressive strength of the hollow ball is more than 3000psi, the prepared buoyancy material can meet the requirement of high pressure resistance (for example, the compressive strength is more than 5.5MPa), so that the service life of the buoyancy material in water is prolonged.
In some embodiments, the wall thickness of the hollow spheres is 0.5 μm to 2.5 μm, and preferably 1 μm to 1.5 μm. When the wall thickness of the hollow ball is 0.5-2.5 μm, the prepared buoyancy material can meet the requirements of high pressure resistance and low density.
These hollow spheres are used in an amount of 20 to 65 parts by weight, and preferably 40 to 60 parts by weight, based on 100 parts by weight of a thermosetting resin described later. When the amount of the hollow spheres used is less than 20 parts by weight, the buoyant material will have an excessively high density and will not meet the specification. When the amount of the hollow sphere used is more than 65 parts by weight, the density of the buoyancy material becomes low and cannot meet the specification.
After the foregoing operation 110, the roughened hollow spheres are subjected to a surface modification step, as shown in operation 120. The surface modification step is to modify the roughened surface of the hollow sphere to increase the wettability of the thermosetting resin added subsequently to the surface of the hollow sphere.
In some embodiments, the surface modification step comprises modifying the roughened surface of the hollow spheres with a silane coupling agent. The silane coupling agent includes silane coupling agents having hydroxyl, alkoxy, amino, epoxy, alkenyl groups and combinations thereof. In some embodiments, the alkoxy groups of the silane coupling agent may react with the silanol groups of the hollow spheres to form silicon-oxygen bonds, thereby reducing the water absorption of the buoyancy material. Specific examples of the silane coupling agent include, but are not limited to, aminopropyltriethoxysilane, tetraethoxysilane, 3-methacryloxypropyltrimethoxysilane, N- β -aminoethyl- γ -aminopropyltrimethoxysilane, γ -aminopropyltriethoxysilane, and (3-glycidoxypropyl) trimethoxysilane, and aminopropyltriethoxysilane is preferable.
In some embodiments, the silane coupling agent is used in an amount of 1 to 10 parts by weight, based on 100 parts by weight of the hollow sphere.
After the foregoing operation 120, the modified hollow spheres, the thermosetting resin, and the metal oxide particles are mixed to obtain a homogenized mixture, as shown in operation 130. In the mixing process, the metal oxide particles belong to the nano grade, so the metal oxide particles can be filled in the gaps between the thermosetting resin and the micron-grade hollow spheres and/or the gaps between the micron-grade hollow spheres to prevent water from entering the gaps, and the water absorption rate of the buoyancy material can be reduced. In some embodiments, the alkoxy groups of the silane coupling agent may react with the metal atoms of the metal oxide particles to form silicon-oxygen-metal bonds, thereby reducing the water absorption of the buoyancy material. In some embodiments, the amine, epoxy and/or alkenyl groups of the silane coupling agent may react with the thermosetting resin.
In some embodiments, the thermosetting resin is mixed with the metal oxide particles prior to the addition of the modified hollow spheres. In other embodiments, the modified hollow spheres and the metal oxide particles are added to the thermosetting resin simultaneously. In some embodiments, the type of resin is a thermosetting resin. In still other embodiments, the order of adding the three is not particularly limited, but the three can be uniformly mixed to achieve the requirement of uniformity of the material of the buoyancy material.
In some embodiments, the mixing can be performed by a mechanical homogeneous stirring method, such as a vacuum stirring method, to uniformly mix the hollow spheres similar to the non-viscous liquid with the thermosetting resin with high viscosity.
In some embodiments, the thermosetting resin comprises an epoxy resin, a phenolic resin, an unsaturated polyester resin, and any combination thereof. Preferably, the thermosetting resin may be an epoxy resin. Further, specific examples of the thermosetting resin may include, but are not limited to, bisphenol a type epoxy resins. Further, in some embodiments, the viscosity of the thermoset at 25 ℃ can be from 1000 cppscs to 2100 cps.
The average particle diameter of the aforementioned metal oxide particles is 5nm to 35nm, and preferably 15nm to 25 nm. When the average particle diameter of the metal oxide particles is less than 5nm, there is a disadvantage in that the specific surface area is too large to cause difficulty in handling in the process of mixing. When the average particle size of the metal oxide particles is greater than 35nm, the excessively large metal oxide particles cannot fill the gap between the thermosetting resin and the hollow sphere, thereby increasing the water absorption rate of the buoyant material.
In some embodiments, the metal oxide particles may comprise particles of oxides of alkali metals, alkaline earth metals, transition metals, and any combination thereof. Further, specific examples of the metal oxide particles may include, but are not limited to, particles of aluminum oxide, zinc oxide, calcium oxide, sodium oxide, magnesium oxide, barium oxide, iron oxide, copper oxide, and tungsten oxide, and preferably aluminum oxide particles.
The metal oxide particles are used in an amount of 0.5 to 4.0 parts by weight, and preferably 2.0 to 4.0 parts by weight, based on 100 parts by weight of the thermosetting resin. When the amount of the metal oxide particles used is less than 0.5 parts by weight, too few metal oxide particles are difficult to fill the voids between the thermosetting resin and the hollow spheres, and it is easy to introduce moisture into the buoyant material, thereby increasing the water absorption thereof, and too large volume of voids will decrease the density of the buoyant material. On the contrary, when the amount of the metal oxide particles is more than 4.0 parts by weight, the excessive metal oxide particles are liable to be aggregated to lower the mixing uniformity of the thermosetting resin, the hollow spheres and the curing agent.
After the aforementioned operation 130, a curing agent is added to the homogenized mixture to perform a curing reaction step, to obtain a buoyant material, as shown in operation 140. The curing agent includes, but is not limited to, amine curing agents, acid anhydride curing agents, and phenol curing agents. The curing agent of the present invention is not particularly limited, and may be one known to those skilled in the art to which the present invention pertains, but it is necessary that the curing agent is capable of causing the aforementioned thermosetting resin to undergo a curing reaction.
The curing agent is used in an amount of 40 to 60 parts by weight, and preferably 45 to 55 parts by weight, based on 100 parts by weight of the thermosetting resin. When the amount of the curing agent used is less than 40 parts by weight, too little curing agent results in incomplete curing of the thermosetting resin and a decrease in the crosslinking density thereof, thereby decreasing the compressive strength of the buoyant material. On the contrary, when the curing agent is used in an amount greater than 60 parts by weight, the excessive curing agent shortens the operation time of the thermosetting resin to which the curing agent is added, which is disadvantageous to injection molding and reduces the uniformity of the material of the buoyant material.
In some embodiments, the thermoset resin, the hollow spheres, the metal oxide particles, and the curing agent are mixed and then injection molded to produce the desired shape of the buoyant material. In other embodiments, after injection molding, pre-cure, high temperature cure (i.e., curing), cooling, and demolding may be optionally performed sequentially. In still other embodiments, post-processing (e.g., cutting and trimming) may be optionally performed after demolding.
The foregoing method of manufacture is to use the composition of the buoyant material of the present invention to manufacture the buoyant material. The composition of the buoyancy material comprises a thermosetting resin, a plurality of hollow spheres, a plurality of metal oxide particles and a curing agent, wherein the description of each component has been detailed in the manufacturing method, and thus the description thereof is omitted.
The water absorption of the buoyancy material prepared by the method is not more than 1% and preferably not more than 0.08% under a 24-hour test, so that the buoyancy material has long-acting low water absorption and can prolong the service life of the buoyancy material.
In some embodiments, the buoyant material has a compressive strength greater than 5.5 MPa. When the compressive strength of the buoyant material is greater than 5.5MPa, the buoyant material has high compressive strength. Compared with the buoyancy material prepared by the common chemical foaming process, the buoyancy material has no problem of creep deformation, so that the buoyancy material has longer service life.
The following examples are provided to illustrate the present invention, but not to limit the invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention.
Manufacture of buoyant materials
Examples
The buoyant material of the example was produced by first producing 100g of hollow glass spheres (average particle diameter (D)50) 30 μm and 1 μm in wall thickness) and water was added for 24 hours under pressure, and the settled hollow glass spheres (i.e., broken hollow glass spheres) were discarded. Then, 500 ml of a 2% aqueous solution of sodium hydroxide was added, and the hollow glass spheres were subjected to alkali washing with ultrasonic waves, followed by water washing and drying. Then, the alkali-washed hollow glass spheres were modified with 60 ml of 20mM aminopropyltriethoxysilane, washed with water and dried to obtain modified hollow glass spheres.
Then, 50g of the modified hollow glass spheres were added in batches to 100g of bisphenol A type epoxy resin which had been uniformly mixed with alumina particles (used in an amount of 2.2g, and having a particle diameter of 20nm) in a vacuum stirring apparatus (the apparatus was maintained at a vacuum degree of 0.01MPa to 0.1 MPa). After mixing and stirring for 20 to 40 minutes, 50g of a curing agent (low viscosity epoxy resin, or please provide the full name of the curing agent) was added, and after mixing and stirring for 5 to 15 minutes, vacuum defoaming (vacuum degree of 0.01MPa to 0.1M Pa) was performed to obtain the composition of the buoyant material of the example.
After the composition described above is poured into a mold coated with a release agent, the resin is allowed to exotherm (i.e., pre-cure) at room temperature. Then, the mixture is cured at a high temperature of 80 ℃ (i.e., curing reaction is performed). After 120 minutes of reaction, the buoyancy material of the example was prepared by cooling and demolding in this order, and the test was conducted in the following evaluation manner.
Comparative example
The comparative example was produced by the same method as in example. Except that, the comparative examples did not use alumina particles, and the specific conditions and test results thereof are shown in table 1 below.
Evaluation method
1. Compressive strength test
The compressive strength test measures uniaxial compressive strength by the ASTM (1621) standard method and evaluates the compressive strength of the buoyant material with the uniaxial compressive strength, wherein when the uniaxial compressive strength is greater than 5.5MPa, the buoyant material is judged to have good compressive strength.
2. Water absorption test
The water absorption test is a test in which the weight (W) of the buoyant material without immersion in water is first measured0). Then, the buoyant material was immersed in water for 30 seconds, then dried, and weighed again to obtain a weight (W) after 30 seconds of immersion1). Then, the buoyant material was immersed in water for 24 hours, then dried, and weighed again to obtain a weight (W) after 24 hours of immersion in water2). Finally, the water absorption (%) after immersion in water for 30 seconds and 24 hours was calculated according to the following formula (I):
wherein WiCan be W1Or W2To calculate the water absorption after 30 seconds or 24 hours of immersion in water.
In addition, the stability of the buoyancy material in water is judged according to the difference between the water absorption rates of 30 seconds and 24 hours, wherein the smaller the difference between the water absorption rates of the two is, the higher the stability of the buoyancy material in water is judged to be.
3. Dielectric constant
The dielectric constant is measured at any 5 positions in the buoyancy material by an ASTM (D2520) standard method, and the difference between the maximum value and the minimum value is calculated to evaluate the uniformity of the material of the buoyancy material, wherein when the difference is not more than 0.5, the material of the buoyancy material is judged to have good uniformity.
4. Observation of microstructures
The microstructure was observed by using a scanning electron microscope to observe the buoyancy material, so as to evaluate the filling state of the metal oxide particles in the gaps between the thermosetting resin and the hollow glass spheres and the gaps between the hollow glass spheres, and the photograph thereof is shown in fig. 2.
5. Measurement of Density
The density is measured by a method customary to those skilled in the art to which the invention pertains.
TABLE 1
N/A indicates that this group of ingredients was not used or that the test was not performed.
Referring to fig. 2, a scanning electron microscope photograph of the buoyancy material of the embodiment is shown. The electron micrograph of the example shows that the voids between the epoxy resin and the hollow glass spheres and the voids between the hollow glass spheres are filled with the alumina particles, so that the microstructure of the buoyancy material of the example is dense.
Further, referring to table 1 above, according to the results of water absorption, the buoyancy material of the example has a smaller water absorption for 30 seconds and 24 hours than the comparative example, and the difference between the water absorption rates is also smaller. Therefore, the alumina particles fill the gaps between the epoxy resin and the hollow glass spheres and the gaps between the hollow glass spheres, so that the water absorption rate of the buoyancy material is reduced, and the stability of the buoyancy material in water is improved.
Secondly, as a result of uniaxial compressive strength (greater than 5.5MPa), the buoyant materials of the examples had high compressive strength. Furthermore, the material of the buoyancy material of the embodiment has good uniformity according to the result of the difference of the dielectric constants (not greater than 0.5).
In summary, the present invention provides a composition of a buoyant material and a method for manufacturing the same, which utilizes surface-roughened hollow microspheres and nano-scale metal oxide particles to prepare a buoyant material having low water absorption, low density and high compressive strength. The coarsening surface of the hollow ball can improve the wettability of the bonding interface of the hollow ball and the thermosetting resin, and the metal oxide particles can be filled in the gap between the thermosetting resin and the hollow ball and the gap between the hollow glass balls so as to reduce the water absorption rate of the buoyancy material, so that the prepared buoyancy material has low water absorption rate and keeps low density and high compressive strength.
Although the present invention has been described with reference to the above embodiments, it should be understood that various changes and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention.
Claims (10)
1. A composition of buoyant materials, comprising:
a thermosetting resin;
a plurality of hollow spheres, wherein the average particle diameter (D) of the plurality of hollow spheres50) Is 10 μm to 100 μm;
a plurality of metal oxide particles, wherein the plurality of metal oxide particles have an average particle size of 5nm to 35 nm; and
a curing agent for curing the epoxy resin composition,
wherein the plurality of hollow spheres is used in an amount of 20 to 65 parts by weight, the plurality of metal oxide particles is used in an amount of 0.5 to 4.0 parts by weight, and the curing agent is used in an amount of 40 to 60 parts by weight, based on 100 parts by weight of the thermosetting resin.
2. The buoyant material composition of claim 1 wherein the thermosetting resin comprises an epoxy resin, a phenolic resin, an unsaturated polyester resin, and any combination thereof.
3. The buoyant material composition of claim 1 wherein said plurality of hollow spheres have a compressive strength greater than 3000 psi.
4. The composition of buoyant material of claim 1 wherein the plurality of hollow spheres have a wall thickness of 0.5 μ ι η to 2.5 μ ι η.
5. A method of making a buoyant material, the method comprising:
a step of roughening the surfaces of the plurality of hollow spheres;
carrying out surface modification on the plurality of roughened hollow spheres;
mixing the modified plurality of hollow spheres, thermosetting resin, and plurality of metal oxide particles to obtain a homogenized mixture; and
adding a curing agent to the homogenized mixture to perform a curing reaction step to obtain the buoyant material;
wherein the average particle diameter (D) of the plurality of hollow spheres50) Is 10 to 100 μm, and the plurality of metal oxide particles have an average particle diameter of 5 to 35 nm.
6. The method of claim 5, wherein the surface roughening step comprises washing the plurality of hollow spheres with a caustic solution.
7. The method of claim 5, wherein the surface modifying step comprises modifying the plurality of hollow spheres with a silane coupling agent.
8. A buoyant material, comprising:
a thermosetting resin;
a plurality of hollow spheres, wherein the average particle diameter (D) of the plurality of hollow spheres50) Is 10 μm to 100 μm; and
a plurality of metal oxide particles at least a portion of which are filled between the plurality of hollow spheres, wherein the plurality of metal oxide particles have an average particle diameter of 5nm to 35 nm;
wherein the water absorption of the buoyant material is no greater than 1%.
9. The buoyant material of claim 8 wherein the buoyant material further comprises bonds formed by reaction of a silane coupling agent with the plurality of hollow spheres and/or bonds formed by reaction of the silane coupling agent with the plurality of metal oxide particles.
10. The buoyant material of claim 8 wherein said plurality of hollow spheres have a compressive strength of greater than 3000 psi.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4598106A (en) * | 1984-11-09 | 1986-07-01 | Nippon Oils & Fats Co., Ltd. | Pressure-resistant buoyancy material |
| US20090038797A1 (en) * | 2007-07-18 | 2009-02-12 | Oxane Materials, Inc. | Proppants With Carbide and/or Nitride Phases |
| JP2012017382A (en) * | 2010-07-07 | 2012-01-26 | Yokohama Rubber Co Ltd:The | Material for forming syntactic foam, and method for producing syntactic foam |
| US20130172448A1 (en) * | 2010-06-24 | 2013-07-04 | Acheron Product Pty Ltd. | Epoxy composite |
| CN103421278A (en) * | 2013-08-10 | 2013-12-04 | 滕州市华海新型保温材料有限公司 | Low-density high-strength solid buoyancy material and preparation method thereof |
| CN106366577A (en) * | 2016-08-30 | 2017-02-01 | 咸宁海威复合材料制品有限公司 | Insulation and heat conduction type buoyancy composite |
| CN106751484A (en) * | 2016-12-05 | 2017-05-31 | 钦州市钦南区生产力促进中心 | A kind of deep-sea High-strength solid buoyancy material and preparation method thereof |
| CN107759206A (en) * | 2017-11-16 | 2018-03-06 | 深圳市大擎科技有限公司 | High-pressure resistant ceramic spherical shell, preparation method and deep-sea buoyant device |
| WO2020135779A1 (en) * | 2018-12-29 | 2020-07-02 | 中国科学院理化技术研究所 | Solid buoyancy material and preparation method therefor and use thereof |
-
2020
- 2020-12-17 CN CN202011493889.3A patent/CN114644809A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4598106A (en) * | 1984-11-09 | 1986-07-01 | Nippon Oils & Fats Co., Ltd. | Pressure-resistant buoyancy material |
| US20090038797A1 (en) * | 2007-07-18 | 2009-02-12 | Oxane Materials, Inc. | Proppants With Carbide and/or Nitride Phases |
| US20130172448A1 (en) * | 2010-06-24 | 2013-07-04 | Acheron Product Pty Ltd. | Epoxy composite |
| JP2012017382A (en) * | 2010-07-07 | 2012-01-26 | Yokohama Rubber Co Ltd:The | Material for forming syntactic foam, and method for producing syntactic foam |
| CN103421278A (en) * | 2013-08-10 | 2013-12-04 | 滕州市华海新型保温材料有限公司 | Low-density high-strength solid buoyancy material and preparation method thereof |
| CN106366577A (en) * | 2016-08-30 | 2017-02-01 | 咸宁海威复合材料制品有限公司 | Insulation and heat conduction type buoyancy composite |
| CN106751484A (en) * | 2016-12-05 | 2017-05-31 | 钦州市钦南区生产力促进中心 | A kind of deep-sea High-strength solid buoyancy material and preparation method thereof |
| CN107759206A (en) * | 2017-11-16 | 2018-03-06 | 深圳市大擎科技有限公司 | High-pressure resistant ceramic spherical shell, preparation method and deep-sea buoyant device |
| WO2020135779A1 (en) * | 2018-12-29 | 2020-07-02 | 中国科学院理化技术研究所 | Solid buoyancy material and preparation method therefor and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| 龙宇飞等: "硅烷偶联剂改性空心玻璃微珠/环氧树脂固体浮力材料的制备及性能研究", 《全面腐蚀控制》, vol. 30, no. 10, pages 17 - 22 * |
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