CN112808998B - Titanium alloy material binder, preparation method thereof, composite material and application - Google Patents
Titanium alloy material binder, preparation method thereof, composite material and application Download PDFInfo
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- CN112808998B CN112808998B CN202011627849.3A CN202011627849A CN112808998B CN 112808998 B CN112808998 B CN 112808998B CN 202011627849 A CN202011627849 A CN 202011627849A CN 112808998 B CN112808998 B CN 112808998B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
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Abstract
The invention relates to the technical field of bonding materials, and particularly discloses a titanium alloy material bonding agent, a preparation method thereof, a composite material and application thereof. The provided preparation method is simple, raw materials are simple and easy to obtain, the production cost is low, and the preparation method is suitable for large-scale production and has wide market prospect.
Description
Technical Field
The invention relates to the technical field of bonding materials, in particular to a titanium alloy material bonding agent, a preparation method thereof, a composite material and application.
Background
With the progress of science and technology and the development of society, the technical field of materials is also rapidly developed. Among them, titanium alloy is an important metal material, which has excellent properties such as high corrosion resistance, small density, high specific strength, good toughness, weldability and the like, and plays an important role in advanced high-tech and advanced-technology fields such as airplanes, aeroengines, airships, satellites, launch vehicles, medical treatment and the like.
At present, because microscopic particles of titanium alloy powder (taking TC4 as an example, the titanium alloy powder has the composition of Ti-6Al-4V, belongs to (alpha + beta) type titanium alloy and has good comprehensive mechanical properties) are spherical, the titanium alloy powder is not easy to form in the preparation process. Generally, titanium alloy powders are mixed with other nanomaterials (e.g. graphene, carbon nanotubes, B) 4 C. SiC, etc.) to aid in the formation of the titanium alloy powder. Generally, binders are largely classified into thermoplastic systems, thermosetting systems, and the like. Multiple experiments show that the existing adhesives such as paraffin, carnauba wax, polypropylene, stearic acid and the like can not effectively form and bond the titanium alloy powder, and meanwhile, a complex degreasing process is required in the preparation process of the thermoplastic system adhesive, so that the cost is high; the thermosetting binder is also in the form of stoneWax, carnauba wax, and stearic acid as main components, and further, EVA (copolymerized from ethylene and acetic acid), glycerin, sugar alcohol, and the like are added, but pores are easily generated inside, although the degreasing time is short, and the performance (hardness, strength, and the like) of the material is reduced to a different extent.
Therefore, the above technical solutions have the following disadvantages in practical use: the binder in the prior art has the problem that the performance of a formed material cannot be guaranteed to be not reduced on the basis of reducing the cost in the forming process of titanium alloy powder, so that the binder in the prior art cannot be suitable for forming titanium alloy materials and other nano materials. To overcome these difficulties, it is desirable to provide a high strength composite metal powder binder.
Disclosure of Invention
The embodiment of the invention aims to provide a titanium alloy material binder, which is used for solving the problem that the performance of a molded material cannot be guaranteed to be not reduced on the basis of reducing the production cost in the process of molding titanium alloy powder in the conventional binder proposed in the background technology.
In order to achieve the above object, the embodiments of the present invention provide the following technical solutions:
a titanium alloy material binder, in particular to a high-strength composite material titanium-based powder binder, which comprises the following raw materials: epoxy resin, strong bonding latex, glycerol, polyvinyl alcohol and a proper amount of water; the strong bonding latex is an organic compound obtained by mixing polyvinyl acetate latex and dibutyl phthalate according to a certain proportion.
As a further scheme of the invention: the raw materials of the titanium alloy material binder also comprise polysulfide rubber, phenolic resin, vinyl resin, silicone resin, furfural resin, polyester resin and the like.
Another object of an embodiment of the present invention is to provide a method for preparing a titanium alloy material binder, including the following steps:
1) weighing polyvinyl alcohol and water according to a ratio, heating the water, adding part of the polyvinyl alcohol, and stirring at a medium speed to obtain a solvent mixture;
2) weighing epoxy resin and strong bonding latex according to a proportion, adding the epoxy resin and the strong bonding latex into the solvent mixture, stirring at a high speed until the epoxy resin and the strong bonding latex are uniformly mixed, then cooling to 45-55 ℃, adding the rest raw materials in sequence, and stirring at a low speed until the mixture is uniformly mixed to obtain a stirred semi-finished product;
3) and standing the stirred semi-finished product in a vacuum environment to obtain a finished product, namely the titanium alloy material binder.
Another object of an embodiment of the present invention is to provide a composite material, in which a raw material of the composite material includes titanium alloy powder and the titanium alloy material binder, and the titanium alloy material binder is used for binding and molding the titanium alloy powder, or for binding and molding the titanium alloy powder and a nanomaterial (for example, graphene, carbon nanotube, B) 4 C. SiC, etc.) for bonding molding.
Another object of an embodiment of the present invention is to provide a use of said composite material in machine manufacturing.
Compared with the prior art, the invention has the beneficial effects that:
the titanium alloy material binder provided by the embodiment of the invention can be used for titanium alloy powder molding, and through the matching of various raw materials such as epoxy resin, strong bonding latex, glycerol, polyvinyl alcohol, water and the like, the crushing performance of the epoxy resin, the bonding performance, the fluidity and the anti-caking performance of the strong bonding latex can be used for titanium alloy powder bonding, so that various performances after molding can be well reflected, the cost is low, the working procedure is simple, a complex degreasing process is not needed, and the problem that the performance of the molded material cannot be guaranteed to be not reduced on the basis of reducing the production cost in the titanium alloy powder molding process of the existing binder is solved. The preparation method of the titanium alloy material binder is simple, the raw materials are simple and easy to obtain, the production cost is low, and the titanium alloy material binder is suitable for large-scale production and has wide market prospect.
Drawings
Fig. 1 is a scanning electron microscope image of the composite material prepared according to one embodiment of the present invention.
Fig. 2 is a partially enlarged view of fig. 1.
Fig. 3 is a hardness curve diagram of composite materials corresponding to different contents of graphene.
FIG. 4 is a scanning electron micrograph of a composite prepared according to another embodiment of the present invention.
Fig. 5 is a partially enlarged view of fig. 4.
FIG. 6 is a graph of hardness curves for composite materials with different carbon nanotube content.
Detailed Description
The invention is described in further detail below with reference to the figures and the specific embodiments. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the concept of the invention. All falling within the scope of the present invention.
The embodiment of the invention provides a titanium alloy material binder, in particular to a high-strength composite material titanium-based powder binder, which comprises the following raw materials: epoxy resin, strong bonding latex, glycerol, polyvinyl alcohol and a proper amount of water; wherein the strong bonding latex is polyvinyl acetate latex and dibutyl phthalate according to a weight ratio of 0.1-1: 0.1-1, and mixing to obtain organic compound.
As another preferred embodiment of the present invention, the weight ratio of the polyvinyl acetate latex to the dibutyl phthalate is 0.1 to 0.5: 0.7-0.9. Of course, the weight ratio of the polyvinyl acetate latex to the dibutyl phthalate may be other ratios, and is selected according to the requirement, and is not limited herein. Preferably, the weight ratio of the polyvinyl acetate latex to the dibutyl phthalate is 0.1: 0.9, in practical application, the existing white latex product is adopted as strong bonding latex, the white latex is one of water-soluble adhesives with the widest application, the largest dosage and the longest history, and is a thermoplastic adhesive prepared by carrying out polymerization reaction on vinyl acetate monomers under the action of an initiator, wherein the dosage of dibutyl phthalate is not excessive and is not more than 10 wt% of polyvinyl acetate monomers.
In another preferred embodiment of the present invention, the softening point of the titanium alloy material binder is above 400 ℃, and the melting point of the titanium alloy material binder is about 450 ℃ and 550 ℃, and is generally about 500 ℃.
As another preferred embodiment of the present invention, the weight ratio of the strongly adhesive latex to the epoxy resin is controlled to be less than 5.5, specifically, to be 2.0 to 5.3.
As another preferred embodiment of the present invention, the weight ratio of the strongly bonding latex to the epoxy resin is controlled to be between 2.2 and 5.
As another preferred embodiment of the present invention, the titanium alloy material binder comprises the following raw materials by weight: 20-40 parts of epoxy resin, 50-70 parts of strong bonding latex, 0.5-1.5 parts of glycerol, 0.5-1.5 parts of polyvinyl alcohol and a proper amount of water.
As another preferred embodiment of the present invention, the raw material of the titanium alloy material binder further includes polysulfide rubber, phenolic resin, vinyl resin, silicone resin, furfural resin, polyester resin, etc., and the total weight of the polysulfide rubber, phenolic resin, vinyl resin, silicone resin, furfural resin, polyester resin is 5 wt% to 15 wt% of the weight of the strong bond latex.
As another preferred embodiment of the present invention, the weight ratio of the polysulfide rubber, the phenol resin, the vinyl resin, the silicone resin, the furfural resin, and the polyester resin is 0.8 to 1.2: 0.8-1.2: 0.8-1.2: 0.8-1.2: 0.8-1.2: 0.8-1.2.
Preferably, the titanium alloy material binder comprises 20-40% of epoxy resin, 50-70% of strong binding latex, about 1% of polyvinyl alcohol, about 1% of glycerol, 1% of polysulfide rubber, 1% of phenolic resin, 1% of vinyl resin, 1% of silicone resin, 1% of furfural resin, 1% of polyester resin and the like, wherein the percentages are weight percentages.
As another preferred embodiment of the present invention, the polyvinyl alcohol is an organic compound, is a white flake, flocculent or powdery solid in appearance, is odorless, is soluble in water (95 ℃ or higher), is slightly soluble in dimethyl sulfoxide, and is insoluble in gasoline, kerosene, vegetable oil, benzene, toluene, dichloroethane, carbon tetrachloride, acetone, ethyl acetate, methanol, ethylene glycol, etc.
In the embodiment of the invention, the titanium alloy material adhesive provided by the embodiment of the invention can be used for effectively bonding titanium alloy powder with high strength, and a titanium alloy plate prepared by using the adhesive has good performance, tight internal structure connection and no gap generation.
The embodiment of the invention also provides a preparation method of the titanium alloy material binder, which comprises the following steps:
1) weighing polyvinyl alcohol and water according to a ratio, heating the water, adding part of the polyvinyl alcohol, and stirring at a medium speed to obtain a solvent mixture;
2) weighing epoxy resin and strong bonding latex according to a proportion, adding the epoxy resin and the strong bonding latex into the solvent mixture, stirring at a high speed until the epoxy resin and the strong bonding latex are uniformly mixed, then cooling to 45-55 ℃, adding the rest raw materials in sequence, and stirring at a low speed until the rest raw materials are uniformly mixed to obtain a stirred semi-finished product;
3) and standing the stirred semi-finished product in a vacuum environment to obtain a finished product, namely the titanium alloy material binder.
It should be noted that, the order of the titanium alloy material binder during the preparation process, specifically, the order of the raw materials addition during the stirring process, is to follow the rule that the dissolution temperature is from high to low.
In another preferred embodiment of the invention, in the preparation method of the titanium alloy material binder, the standing is specifically to stand for a period of time after the raw materials are mixed, and then the titanium alloy material binder is placed in a vacuum environment for 0.5 to 2 hours.
In another preferred embodiment of the present invention, in the method for preparing the titanium alloy material binder, under the condition that the temperature is reached, the polyvinyl alcohol is dissolved in water after swelling, and the addition amount is controlled to be less than 1.5% of the total mass.
In another preferred embodiment of the present invention, in the preparation method of the titanium alloy material binder, the stirring speed is ensured to be stable during the stirring process, and the error of the high speed, the medium speed and the low speed is within 10% within a reasonable range respectively.
In another preferred embodiment of the invention, in the preparation method of the titanium alloy material binder, when the binder is placed in a vacuum environment, the tightness of the vacuum environment should be lower than 0.300KPa/min to ensure the defoaming effect.
As another preferred embodiment of the invention, in the preparation method of the titanium alloy material binder, the viscosity of the titanium alloy material binder is controlled to be 2500-5500 mpa.s.
As another preferred embodiment of the invention, in the preparation method of the titanium alloy material binder, the stirring speed of the low-speed stirring is 500-1000r/min, and the time is controlled to be 0.3-1 h; the stirring speed of the medium-speed stirring is 1000-; the stirring speed of the high-speed stirring is 1500-.
The preparation method of the titanium alloy material binder is mainly characterized in that different-speed dispersing mixers are adopted for multiple-cycle mixing:
preferably, firstly, stirring at a medium speed for 0.3-2 h;
preferably, then, the mixture is stirred at high speed, and the time is controlled to be 0.5 to 1.5 hours;
preferably, finally, stirring at low speed for 0.3-1 h;
preferably, the medium-speed stirring in the first step is to ensure that the solute (polyvinyl alcohol) and the solvent (water) are uniformly mixed and then dissolved; the second step of high-speed stirring operation is to ensure that bubbles are reduced during solid solution and soften the mixed stirred body; and thirdly, stirring at a low speed is performed to ensure complete dissolution, so that the phenomenon of overhigh stirring energy consumption is avoided, and the change state of the binder can be clearly seen from the macroscopic view.
In another preferred embodiment of the invention, in the preparation method of the titanium alloy material binder, along with the increase of the stirring speed and the increase of the stirring time, the inside of the semi-finished product and the paddle of the stirrer are in continuous contact and friction, the temperature of the binder is slightly increased, and in order to ensure that excessive local chemical side reactions do not occur in the binder, after the middle period of high-speed stirring, the temperature is preferably ensured to be stable by adopting an air cooling or circulating water cooling mode and is controlled to be between 25 ℃ and 35 ℃.
The embodiment of the invention also provides the titanium alloy material binder prepared by the preparation method of the titanium alloy material binder.
The embodiment of the invention also provides application of the titanium alloy material binder in titanium alloy powder molding.
The embodiment of the invention also provides a composite material, which comprises titanium alloy powder and the titanium alloy material binder, wherein the titanium alloy material binder is used for bonding and molding the titanium alloy powder or bonding and molding the titanium alloy powder and a nano material (such as graphene, carbon nano tubes and B) 4 C. SiC, etc.) are bonded and molded. The crushing performance of the epoxy resin, the adhesive property, the fluidity and the anti-caking performance of the strong adhesive latex are used for bonding the titanium alloy powder, so that various performances after the titanium alloy powder is formed can be well reflected.
As another preferred embodiment of the present invention, in the composite material, the added amount of the nanomaterial is 0.2 wt% to 2 wt% of the weight of the titanium alloy powder.
As another preferred embodiment of the present invention, since titanium alloy powder is microscopically visible as spherical particles, and is not easily bonded in the blank preparation process, although some of the existing bonding agent technologies can be satisfied, there are many side reactions, complicated processes, or various properties of the titanium-based plate are reduced to different degrees after the finished product, for example, in the existing technology, "an epoxy-graphene metal bonding agent and a preparation method thereof" disclosed in chinese patent CN2017104980977 is that graphene is dispersed in an epoxy resin matrix by means of mechanical blending and ultrasonic blending, so as to prepare a bonding agent having very high tensile shear strength to different substrates; the 'metal binder with environmental universality and the preparation method thereof' disclosed by the Chinese patent CN2019100906447 are characterized in that a reaction mixture of a tea phenol derivative and graphene oxide is added into epoxy resin, so that the interaction force between the binder and the metal surface is improved, and the metal binder which can be used in a dry environment and a water environment is obtained; the 'metal binder' disclosed in the Chinese patent CN2017111825711 is a binder which is high in water resistance, acid resistance, alkali resistance and temperature resistance and good in resistance and is prepared by a preparation method of mainly mixing a plurality of organic matters and adding an inorganic matter as an auxiliary.
According to the technical scheme, titanium alloy powder cannot be effectively molded and bonded, a complex degreasing process is needed in the preparation process of the thermoplastic system bonding agent, the cost is high, or although the degreasing time is short, pores are easily generated in the thermoplastic system bonding agent, and the strength of the material is reduced to different degrees. Therefore, the invention provides the titanium alloy material adhesive which has simple working procedures, low cost and low influence on the performance of the plate, and the titanium alloy material adhesive can effectively carry out high-strength bonding on the titanium alloy powder by mixing with the titanium alloy powder, standing for a specific time after mixing, and generally standing for 48-72 hours in a dry ventilation environment.
The embodiment of the invention also provides an application of the composite material in mechanical manufacturing.
As another preferred embodiment of the present invention, the application may be used in modern aircraft manufacturing, such as aircraft engine components, frameworks, fastening devices for aircraft joints, and the like, or in ship manufacturing, submarine manufacturing, and the like, which are selected according to requirements, and are not limited herein.
The technical effects of the titanium alloy material binder of the present invention will be further described below by referring to specific examples.
The model of an instrument required by Scanning Electron Microscope (SEM) analysis is EVO MA 10, elements contained in the surface of a sample are analyzed through the SEM, and counting values of the elements at different distances are analyzed through energy spectrum lines. The hardness test was carried out using a model HV-1000Z digital microscope. Hardness test the test force applied was 500gf (4.96N), the load retention time was 10s, seven points were measured for each sample, the maximum and minimum values were excluded, and the average value of the remaining five points was taken. The hardness test comprises the following specific operation steps:
(1) placing the surface to be tested of the sample to be tested on a test workbench in an upward mode, and turning on a hardness test power supply;
(2) selecting the required loading force 500gf, and setting the load retention time which is 10 s;
(3) clicking a loading button to automatically load the equipment;
(4) after loading is finished, observing the sample by using a 400-time objective lens, finding out four indentation vertexes, measuring the length of an indentation diagonal line by using a micrometer caliper on an eyepiece, inputting the length on a small screen, automatically popping up a corresponding hardness value by equipment, and finally finishing testing and recording a result.
Example 1
The titanium alloy material binder comprises the following raw materials: 35 +/-5 kg of epoxy resin, 60 +/-7 kg of strong bonding latex, 1 kg of glycerol, 1 kg of polyvinyl alcohol, 1 kg of polysulfide rubber, 1 kg of phenolic resin, 1 kg of vinyl resin, 1 kg of silicone resin, 1 kg of furfural resin, 1 kg of polyester resin and a proper amount of ultrapure deionized water.
In this embodiment, the preparation method of the titanium alloy material binder includes the following steps:
a. weighing the following raw materials according to the process proportion for preparing the binder: epoxy resin, strong adhesive latex, glycerin, polyvinyl alcohol, polysulfide rubber, phenolic resin, vinyl resin, silicone resin, furfural resin, polyester resin, and a proper amount of water. Adding boiling ultrapure deionized water as a solvent and a part of polyvinyl alcohol into a stirring vessel, starting a stirring device, and stirring at a medium speed of 1300r/min for 20 min.
b. Adding the needed strongly bonded latex, epoxy resin and glycerol into a solvent, and stirring at a high speed for 1.2h, wherein the rotating speed is 1800 r/min; stirring for 0.6h at low speed of 800r/min to obtain a stirred mixture.
c. Adding the rest raw materials into the stirred mixture, continuously stirring, and stirring at the medium speed for 0.5h at the rotating speed of 1300 r/min; stirring at high speed for 1h at 1800r/min, and stirring at medium speed for 0.4h at 1300r/min to obtain colloid.
d. And defoaming the prepared colloid for 1h in a vacuum state to obtain the titanium alloy material binder.
Example 2
The finished product of the titanium alloy material binder in example 1, TC4 powder and graphene material were uniformly mixed (the addition amounts of the graphene material were 0.2 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, and 2 wt% of the weight of TC4 powder, respectively), placed in a dry and ventilated place for 55 hours, pressed, sintered, and tested by SEM and hardness analysis device.
Specifically, mixed powder of TC4 powder and a graphene material, which is ball-milled by a ball mill, is placed into a ball milling tank, and then 3-4 spoons (about 5 +/-4 grams) of the prepared titanium alloy material binder are taken out by a small medicine spoon and added into the ball milling tank filled with the mixed powder. And stirring by using a glass rod to ensure that the mixed powder is fully contacted with the titanium alloy material binder, and stirring to finally form a dough. And finally, filling the mixed powder and the titanium alloy material binder into a sealed bag to be stored for 2-3 days.
And after the above process is finished, starting the pressing step in a positive mode. The material of the die required by pressing is tool steel, the maximum pressure born by the die is about 100MPa, the actual applied pressure is 15MPa, the standing time is about 30s, the die is removed, the pressing is finished, and then the obtained sample is sintered. In the sintering process, a sample is required to be placed in a crucible, a box-type atmosphere furnace is adopted as a sintering device, air in a hearth is pumped out by using a vacuum pump, and then argon is introduced. The argon gas is mainly used for exhausting residual air in the hearth. When the gas pressure of the door of the box-type atmosphere furnace reaches 0.05, the ventilation is stopped. After all preparations are finished, opening a switch of the box-type atmosphere furnace, setting the starting temperature to be 50 ℃, the ending temperature to be 1250 ℃, averagely heating up to 10 ℃/min, preserving heat for two hours, and finally cooling along with the furnace. After cooling, the sample is taken out, and SEM and hardness analysis are performed on the obtained sample, and the specific results are shown in fig. 1 to 3, wherein fig. 1 is a scanning electron microscope picture of the composite material prepared according to the embodiment of the present invention, and fig. 2 is a partially enlarged view of fig. 1. Fig. 3 is a hardness curve diagram of composite materials corresponding to different contents of Graphene (GR).
As can be seen from the SEM image, the spheres are connected more tightly, and there is a shiny material in the gaps between the spheres. From the energy spectrum, it was found that V, O, C element was relatively stable and fluctuation of Ti element was large, and it was analyzed that Al element was precipitated in the gaps between the spheres but no Al element precipitated was reacted with C element in the gaps to form a new compound. The TC4 without added graphene has the advantages that the preferred growth mode of crystal grains is changed due to the absence of graphene and TiC; and the TC 4/graphene composite material has the defects that the recrystallization is hindered by the graphene existing in the middle and partial TiC, so that the crystal grain growth is not obvious. Moreover, the tissue is intact in the figure, and no tissue defects or holes appear. The method is shown to be capable of well bonding TC4 powder, and the bonding agent is smoothly decomposed without generating redundant byproducts in the high-temperature sintering process.
As can be seen from fig. 3, the hardness of the TC4 powder mixed with graphene was improved as compared with that of TC4 alone, and the hardness value varied with the amount of graphene mixed in the TC4 titanium alloy. The average hardness of a sample mixed with 1% graphene in the TC4 titanium alloy is the lowest; while the sample mixed with 2% graphene has the highest average hardness. It is shown that the addition of a small amount of GR has a significant enhancing effect on the hardness of TC 4. The reason why the hardness is increased is that the GR is embedded in the matrix, the lattice constant of the surrounding matrix is changed, and in addition, part of TiC is generated, and together with the GR, the movement of dislocations is inhibited, and a large number of dislocations are accumulated in the portion where they contact each other, thereby increasing the hardness. While GR has a GR content of 1%, the hardness of GR is reduced in internal cluster, but at a GR content of 2%, the internal GR content is high, and the cluster reaches or exceeds a limit value, reacts with Ti to form TiC, and the hardness of TiC is second only to diamond, so the hardness increases at 2%.
Example 3
The titanium alloy material binder comprises the following raw materials: 30 +/-5 kg of epoxy resin, 55 +/-6 kg of strong bonding latex, 1 kg of glycerol, 1 kg of polyvinyl alcohol, 1 kg of polysulfide rubber, 1 kg of phenolic resin, 1 kg of vinyl resin, 1 kg of silicone resin, 1 kg of furfural resin, 1 kg of polyester resin and a proper amount of ultrapure deionized water.
In this embodiment, the preparation method of the titanium alloy material binder includes the following steps:
a. weighing the following raw materials according to the process proportion for preparing the binder: epoxy resin, strong adhesive latex, glycerin, polyvinyl alcohol, polysulfide rubber, phenolic resin, vinyl resin, silicone resin, furfural resin, polyester resin, and a proper amount of water. Adding boiling ultrapure deionized water as a solvent and a part of polyvinyl alcohol into a stirring vessel, starting a stirring device, and stirring at a medium speed of 1300r/min for 20 min.
b. Adding the needed strong bonding latex, epoxy resin and glycerol into a solvent, and stirring at a high speed for 1h, wherein the rotating speed is 1630 r/min; stirring at medium speed for 0.4h at the rotation speed of 1150r/min to obtain a stirred mixture.
c. Adding the rest raw materials into the stirred mixture, continuously stirring, and stirring at low speed for 0.5h at the rotating speed of 850 r/min; stirring at 1650r/min for 1h at high speed, and stirring at 1200r/min for 0.4h at medium speed to obtain colloid.
d. And defoaming the prepared colloid for 50h in a vacuum state to obtain the titanium alloy material binder.
Example 4
The finished product of the titanium alloy material binder in example 3, TC4 powder and a carbon nanotube material (the addition amount of the carbon nanotube material is 0.2 wt%, 0.5 wt%, 1 wt%, 1.5 wt% and 2 wt% of the weight of the TC4 powder respectively) are uniformly mixed, placed in a dry and ventilated place for 60 hours, pressed, sintered and molded, and the finished product of the composite material is detected by an SEM and a hardness analysis device.
Specifically, mixed powder of TC4 powder and a carbon nanotube material, which is ball-milled by a ball mill, is put into a ball milling tank, and then 3-4 spoons (about 5 +/-4 grams) of the prepared titanium alloy material binder are taken out by a small medicine spoon and added into the ball milling tank filled with the mixed powder. And stirring by using a glass rod to ensure that the mixed powder is fully contacted with the titanium alloy material binder, and stirring to finally form a dough. Finally, the mixed powder and the titanium alloy material binder are evenly mixed, and the obtained bulk is put into a sealed bag to be stored for 2-3 days.
And after the process is finished, starting the step of pressing in a positive mode. The material of the die required by pressing is tool steel, the maximum pressure born by the die is about 100MPa, the actual applied pressure is 15MPa, the standing time is about 30s, the die is removed, the pressing is finished, and then the obtained sample is sintered. During the sintering process, a sample is required to be placed in a crucible, the adopted sintering device is a box-type atmosphere furnace, air in a hearth is pumped out by using a vacuum pump, and then argon is introduced. The argon gas is mainly used for exhausting residual air in the hearth. When the gas pressure of the door of the box-type atmosphere furnace reaches 0.05, the ventilation is stopped. After all preparations are finished, opening a switch of the box-type atmosphere furnace, setting the starting temperature to be 50 ℃, the ending temperature to be 1250 ℃, averagely heating up to 10 ℃/min, preserving heat for two hours, and finally cooling along with the furnace. After cooling, the sample was taken out, and SEM and hardness analysis were performed on the obtained sample, and the specific results are shown in fig. 4 to 6, wherein fig. 4 is a scanning electron microscope picture of the composite material prepared by the embodiment of the present invention, and fig. 5 is a partially enlarged view in fig. 4. Fig. 6 is a graph of the hardness of composites using different amounts of Carbon Nanotubes (CNTs).
As can be seen from the SEM image, the balls are connected more tightly, and the brightness is more evident at the gaps than in fig. 1. It can be concluded that there is a flow of metal elements into the gap and a depression due to uneven forces during powder compaction. According to the energy spectrogram, the curve fluctuation range of the three elements of Ti, Al and C is large, and the curves of the other two elements are relatively stable. Meanwhile, the following conclusions can be drawn through the energy spectrum diagram: it was judged that the Al element in the sample partially flowed into the gap. However, it cannot be said that Al and C in the gap must react to form a new compound. TC4 without added CNT changes its grain preferred growth mode due to the absence of CNT and TiC; in the TC4/CNT composite material, however, the CNT is present in the middle and part of TiC hinders recrystallization, so that the crystal grain growth is not significant, and thus the change in diffraction peak is not significant. Meanwhile, the CNT in the TC4/CNT composite material and part of TiC promote the recrystallization of TiO2, so that more obvious grain growth is caused.
As can be seen from fig. 6, the TC4 powder mixed with the carbon nanotubes has an increased hardness as compared to TC4 alone, and the hardness value varies with the amount of the carbon nanotubes mixed in the TC4 titanium alloy. Wherein, when 0.5 percent of carbon nano-tubes are mixed in the TC4 titanium alloy, the hardness value reaches the highest value. It is shown that the addition of a certain amount of CNT has a significant enhancing effect on the hardness of TC 4. The reason why the hardness is enhanced is that the C atoms in the CNT are embedded in the matrix, the lattice constant of the surrounding matrix is changed, and a part of TiC is generated to hinder the movement of dislocations together with the CNT, so that a large number of dislocations are accumulated at the portions where they contact each other, thereby increasing the hardness. While the hardness gradually decreases with an increase in the CNT content because the CNTs have undergone cluster, resulting in a decrease in hardness, while GR has reached a maximum at around 1.5% of cluster amount, but since the CNT specific surface area is greater than GR, the cluster amount has not reached the maximum at a CNT content of 2% and the hardness value has been decreasing. However, as the content of CNTs continues to increase, there may be a tendency for the hardness to increase gradually, as the amount of CNT clusters reaches, and even exceeds, the limit value. In this case, TiC is generated in a large amount, and in addition, the CNT itself has a strong hardness, so that the hardness may be increased.
Example 5
The titanium alloy material binder comprises the following raw materials: 35 kg of epoxy resin, 60 kg of strong bonding latex (adopting the existing white latex product), 1 kg of glycerin and 1 kg of polyvinyl alcohol.
In the embodiment of the invention, the preparation method of the titanium alloy material adhesive specifically comprises the following steps:
a. weighing the following raw materials according to the process proportion for preparing the binder: epoxy resin, strong adhesive latex, glycerol, polyvinyl alcohol and a proper amount of water. Adding boiling ultrapure deionized water as a solvent and part of polyvinyl alcohol into a stirring vessel, starting a stirring device, and stirring at a medium speed of 1300r/min for 20 min.
b. Adding the needed strong bonding latex, epoxy resin and glycerol into a solvent, and stirring at a high speed of 1800r/min for 1.2h to obtain a stirring mixture.
c. Cooling to 50 deg.C, adding the rest raw materials into the stirred mixture, stirring at high speed of 1800r/min for 1h, and stirring at low speed of 700r/min for 0.4h to obtain colloid.
d. And defoaming the prepared colloid for 1h in a vacuum state to obtain the titanium alloy material binder.
Example 6
The temperature was reduced to 45 ℃ as compared with example 5, and the same procedure as in example 5 was repeated.
Example 7
The temperature was reduced to 55 ℃ as compared with example 6, and the temperature was the same as example 6.
Example 8
Compared with the example 6, the stirring speed of the low-speed stirring is 500r/min, and the time is controlled to be 0.3 h; the stirring speed of the medium-speed stirring is 1000r/min, and the time is controlled to be 0.3 h; the stirring speed of the high-speed stirring is 1500r/min, the time is controlled to be 0.5h, and the rest is the same as that of the embodiment 6.
Example 9
Compared with the example 6, the stirring speed of the low-speed stirring is 1000r/min, and the time is controlled to be 1 h; the stirring speed of the medium-speed stirring is 1500r/min, and the time is controlled to be 2 h; the stirring speed of the high-speed stirring is 2000r/min, the time is controlled to be 1.5h, and the rest is the same as that of the embodiment 6.
Example 10
Compared with the example 6, the stirring speed of the low-speed stirring is 750r/min, and the time is controlled to be 0.7 h; the stirring speed of the medium-speed stirring is 1250r/min, and the time is controlled to be 1.1 h; the stirring speed of the high-speed stirring is 1750r/min, the time is controlled to be 1h, and the rest is the same as that of the embodiment 6.
Example 11
Compared to example 6, except that the strongly bonding latex is polyvinyl acetate latex and dibutyl phthalate in a weight ratio of 0.1: the same procedure as in example 6 was repeated except that the organic formulation obtained was mixed in the ratio of 1.
Example 12
Compared to example 6, except that the strongly bonding latex was polyvinyl acetate latex and dibutyl phthalate in a weight ratio of 1: the same procedure as in example 6 was repeated except that the organic formulation obtained was mixed in an amount of 0.1.
Example 13
Compared to example 6, except that the strongly bonding latex was a polyvinyl acetate latex and dibutyl phthalate at a weight ratio of 0.1: the same procedure as in example 6 was repeated except that the organic formulation obtained was mixed in an amount of 0.7.
Example 14
Compared to example 6, except that the strongly bonding latex was polyvinyl acetate latex and dibutyl phthalate in a weight ratio of 0.5: the same procedure as in example 6 was repeated except that the organic formulation obtained was mixed in an amount of 0.9.
Example 15
The titanium alloy material binder comprises the following raw materials: 20 kg of epoxy resin, 50 kg of strong adhesive latex, 0.5 kg of glycerin, 0.5 kg of polyvinyl alcohol and a proper amount of water. In this example, the preparation method of the titanium alloy material binder was the same as that of example 13.
Example 16
The titanium alloy material binder comprises the following raw materials: 40 kg of epoxy resin, 70 kg of strong adhesive latex, 1.5 kg of glycerol, 1.5 kg of polyvinyl alcohol and a proper amount of water. In this example, the preparation method of the titanium alloy material binder was the same as that of example 13.
Example 17
The same as example 6 was repeated, except that the epoxy resin was 35 kg and the strongly bonding latex was 70 kg, as compared with example 6.
Example 18
The same as example 6 was repeated except that the epoxy resin was 10 kg and the strongly adhesive latex was 53 kg as compared with example 6.
Example 19
The same as example 6 was repeated except that the epoxy resin was 10 kg and the strongly adhesive latex was 50 kg, as compared with example 6.
Example 20
The same as example 6 was repeated, except that the epoxy resin was 20 kg and the strong adhesive latex was 44 kg, as compared with example 6.
Example 21
The procedure of example 6 was repeated, except that the raw materials of the titanium alloy material binder included polysulfide rubber, phenol resin, vinyl resin, silicone resin, furfural resin, and polyester resin in equal weight amounts, and the total weight of the polysulfide rubber, phenol resin, vinyl resin, silicone resin, furfural resin, and polyester resin was 5 wt% of the weight of the high-strength binder latex.
Example 22
The procedure of example 6 was repeated, except that the raw materials of the titanium alloy material binder included polysulfide rubber, phenol resin, vinyl resin, silicone resin, furfural resin, and polyester resin in equal weight amounts, and the total weight of the polysulfide rubber, phenol resin, vinyl resin, silicone resin, furfural resin, and polyester resin was 15 wt% of the weight of the high-strength binder latex.
Example 23
Compared to example 22, except that the weight ratio of polysulfide rubber, phenol resin, vinyl resin, silicone resin, furfural resin, polyester resin was 0.8: 1.2: 1.2: 1.2: 1.2: 1.2, the same as example 22.
Example 24
Compared to example 22, except that the weight ratio of polysulfide rubber, phenol resin, vinyl resin, silicone resin, furfural resin, polyester resin was 1.2: 0.8: 0.8: 0.8: 0.8: the procedure of example 22 was repeated except for 0.8.
The titanium alloy material binder provided by the embodiment of the invention is used as a high-strength composite material titanium-based powder binder, and is characterized by low cost, simple process and no need of complex degreasing process, and can effectively bond titanium alloy powder with high strength.
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (9)
1. The composite material is characterized in that raw materials of the composite material comprise titanium alloy powder and a titanium alloy material binder, wherein the titanium alloy material binder is used for bonding and molding the titanium alloy powder or bonding and molding the titanium alloy powder and a nano material; the titanium alloy material binder comprises the following raw materials: epoxy resin, strong bonding latex, glycerol, polyvinyl alcohol and a proper amount of water; wherein the strong bonding latex is polyvinyl acetate latex and dibutyl phthalate according to a weight ratio of 0.1-1: mixing at a ratio of 0.1-1.
2. The composite material as claimed in claim 1, wherein the softening point of the titanium alloy material binder is 400 ℃ or higher, and the melting point of the titanium alloy material binder is 450-550 ℃.
3. The composite material of claim 1, wherein the weight ratio of the strongly bonding latex to the epoxy resin is between 2.0 and 5.3.
4. The composite material of claim 1, wherein the titanium alloy material binder comprises the following raw materials in parts by weight: 20-40 parts of epoxy resin, 50-70 parts of strong bonding latex, 0.5-1.5 parts of glycerol, 0.5-1.5 parts of polyvinyl alcohol and a proper amount of water.
5. The composite material of claim 4, wherein the raw materials of the titanium alloy material binder further comprise polysulfide rubber, phenolic resin, vinyl resin, silicone resin, furfural resin, and polyester resin, and the total weight of the polysulfide rubber, phenolic resin, vinyl resin, silicone resin, furfural resin, and polyester resin is 5 wt% to 15 wt% of the weight of the high-power bonding latex.
6. The composite material as claimed in any one of claims 1 to 5, wherein the preparation method of the titanium alloy material binder comprises the following steps:
1) weighing polyvinyl alcohol and water according to a ratio, heating the water, adding part of the polyvinyl alcohol, and stirring at a medium speed to obtain a solvent mixture;
2) weighing epoxy resin and strong bonding latex according to a proportion, adding the epoxy resin and the strong bonding latex into the solvent mixture, stirring at a high speed until the epoxy resin and the strong bonding latex are uniformly mixed, then cooling to 45-55 ℃, adding the rest raw materials, and stirring at a low speed until the epoxy resin and the strong bonding latex are uniformly mixed to obtain a semi-finished product;
3) and standing the semi-finished product in a vacuum environment to obtain the titanium alloy material binder.
7. The composite material as claimed in claim 6, wherein in the preparation method of the titanium alloy material adhesive, the stirring speed of the low-speed stirring is 500-1000 r/min; the stirring speed of the medium-speed stirring is 1000-; the stirring speed of the high-speed stirring is 1500-2000 r/min.
8. The composite material of claim 1, wherein the nanomaterial is added in an amount of 0.2 wt% to 2 wt% based on the weight of the titanium alloy powder.
9. Use of a composite material according to claim 1 or 8 in mechanical manufacture.
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| JP3443742B2 (en) * | 1992-11-09 | 2003-09-08 | 三東商事株式会社 | Layered molded body |
| ES2243456T3 (en) * | 2000-01-25 | 2005-12-01 | Glatt Systemtechnik Dresden Gmbh | HOLLOW SPHERES AND PROCEDURE FOR MANUFACTURING HOLLOW SPHERES AND LIGHT STRUCTURAL COMPONENTS WITH HOLLOW SPHERES. |
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