CN111378248A - Preparation method of metal-based high polymer material, preparation method of composite material and prepared mold - Google Patents
Preparation method of metal-based high polymer material, preparation method of composite material and prepared mold Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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- 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
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention belongs to the technical field of composite materials, and particularly relates to a preparation method of a metal-based high polymer material, which comprises the following steps: adding epoxy resin into a reaction kettle, heating and dispersing uniformly; adding 5-10 parts of modified epoxy resin; adding an epoxy diluent and a dispersant; adding an anti-settling auxiliary agent; adding a polymerization assistant; adding a defoaming agent; mixing Ti, iron oxide powder, electrolytic iron powder, reduced iron powder, carbon black, Cr, Mn, Mg, Zn, Wc, Al and ceramic micro powder to form metal mixed powder; and adding the metal mixed powder into the resin mixed solution, stirring and defoaming. The composite material is prepared through mixing curing agent with polymer material, stirring, initial curing at 20-35 deg.c and post curing at 80-160 deg.c. The mold is made of polymer composite materials. The prepared die has high strength and hardness, small contractibility and good sedimentation resistance.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a preparation method of a metal-based high polymer material, a preparation method of a composite material and a mold thereof.
Background
The trial production of automobile products generally occurs when a whole automobile enterprise needs to release a brand new automobile type or change or upgrade an original automobile type. The trial production objects of the automobile products mainly refer to sample automobiles, automobile bodies, local automobile bodies, internal and external ornaments and parts. The trial-manufacturing sample car generally comprises a concept car, a verification car and a test car, and the concept design focuses more on appearance and shape; the design and trial production of the verification vehicle and the test vehicle more emphasize reasonable size, qualified quality and the like; in the trial-manufacturing sample car, most trial-manufactured parts are formed by stamping and sheet metal parts, and the cold stamping forming technology is generally adopted to form all metal trial-manufacturing sample parts. As whole car manufacturing enterprises launch new car models with shorter and shorter cycle and fast take the market of brand goods. In order to reduce the development period and cost at this stage and improve the timeliness and cost competitiveness of the product, there is a development of rapid mold technology. The Rapid Tooling technology (Rapid Tooling-RT) is a new method and a new process for rapidly manufacturing a mold developed from Rapid Prototyping-RP. A Prototype Vehicle (Prototype Vehicle) is a Prototype Vehicle manufactured in the process of developing a new Vehicle type. The sample vehicle trial production is to perform various evaluations, performance tests, improvements and the like on a new vehicle type by manufacturing a sample vehicle. After the model design and the design of the vehicle body parts are basically finished, a vehicle manufacturer performs a small number of sample vehicles on trial according to design data, finds out the defects of the sample vehicles through test evaluation, improves the design and then manufactures the next version of the sample vehicles. Generally, a new vehicle type can be put into production qualitatively only through a plurality of trial-production and tests of sample vehicles. The sample vehicle is divided into a concept vehicle, a verification vehicle and a test vehicle. The trial production of the sample car mainly has the following purposes:
1. the precision is ensured and the cost is reduced by actually processing, manufacturing, verifying and improving the processing technology;
2. through tests and improved design, the performance and reliability of each part and the whole vehicle of a mass production vehicle are ensured;
3. through the display of the sample vehicle, the market and the consumer reaction are explored, useful reference is provided for postnatal propaganda and sales strategies, and the market risk is avoided.
The main materials used in the prior rapid trial-manufacturing mold are as follows: gray cast iron (FC30), plain steel, Zinc Alloy (ZAS), polymer alloy;
gray cast iron (FC 30): the casting process has serious pollution, high energy consumption, long period, difficult processing, higher and higher comprehensive cost and low strength and fatigue;
the common problems of the high molecular alloy dies in the current market are that the die hardness is insufficient, the number of the metal plate pressing pieces is less than 200, and the economic scale cannot be achieved;
the alloy material is high in cost, the zinc-based alloy (ZAS) of the rapid trial-manufacture die is a recyclable die material, the die material is melted and melted at 550 ℃ and is melted and melted again, the casting period is about one week faster than that of FC30, but the hardness is lower, about 100 stamping parts need die repair, thin and shallow parts can be adopted, and the low-melting-point alloy material is low in strength (the tensile strength is only about 60 MPa), so that the zinc-based alloy is not very suitable for plates with the plate thickness of more than 1.5 mm.
Disclosure of Invention
In order to solve the above technical problem, the present invention adopts the following aspects.
In a first aspect:
a preparation method of a metal-based high polymer material comprises the following steps:
step S01, adding 5-10 parts of epoxy resin into a reaction kettle, heating to 90-100 ℃, and heating and stirring until the epoxy resin is uniformly dispersed;
step S02, after the temperature is raised to 100 ℃ and stabilized, adding 5-10 parts of modified epoxy resin, and stirring uniformly;
step S03, adding 6.6-12 parts of epoxy diluent until the mixture is uniformly stirred;
step S04, adding 0.2-0.5 part of dispersing agent until the mixture is uniformly stirred;
step S05, adding 0.2-0.5 part of anti-settling auxiliary agent until the mixture is uniformly stirred;
step S06, adding 1-2 parts of polymerization auxiliary agent, and stirring uniformly;
step S07, adding 2-5 parts of defoaming agent until the mixture is uniformly stirred;
step S08, mixing 6-8 parts of Ti, 3-8 parts of 2000-mesh iron oxide powder, 1-3 parts of 1200-mesh iron oxide powder, 3-4 parts of 1600-mesh electrolytic iron powder, 1-5 parts of 1600-mesh reduced iron powder, 3-6 parts of 800-mesh reduced iron powder, 3-4 parts of 600-mesh carbon black, 4-7 parts of Cr, 3-7 parts of Mn, 5-7 parts of Mg, 1-5 parts of Zn, 1-5 parts of Wc, 1.5-3.5 parts of Al and 3-8.5 parts of ceramic micro powder to form metal mixed powder;
adding the metal mixed powder into the resin mixed liquid prepared in the step S07 until the powder is uniformly stirred to be fluid;
step S09 is to defoam the uniformly stirred fluid material to obtain a fluid metal-based polymer material.
Further, in step S08, the metal mixed powder is mixed with 2 to 3 parts of a metal surface treatment agent and is sprayed and stirred in advance to obtain a pretreated metal mixed powder, and then the pretreated metal mixed powder is added into the resin mixed liquid and is stirred uniformly.
Further, adding 5-10 parts of graphene resin solution into the pretreated metal mixed powder in the adding process;
the graphene resin solution comprises the following components in parts by weight:
2 to 3 parts of a graphene dispersion, and
90-100 parts of epoxy resin.
In a second aspect:
a composite material preparation method comprises the following steps:
step P1, 1-2 parts of curing agent are taken and matched with 9-10 parts of high polymer material until being uniformly mixed;
step P2, controlling the temperature at 20-35 ℃ for 3-5 hours to obtain a primarily cured polymer composite material;
and step P3, controlling the temperature of the preliminarily cured polymer composite material at 80-160 ℃ for 6-9 hours to obtain the finished polymer composite material.
A third aspect;
a mould is made of the polymer composite material prepared by the composite material preparation method.
The beneficial effect of the invention is that,
the die prepared by the metal-based high polymer material preparation method and the composite material preparation method has the following advantages;
1. the mold prepared by using the metal-based polymer composite material has the characteristics of low expansion coefficient and high hardness (HRC: 48-53), the shrinkage rate of the resin material is only one to five ten thousandths, the quality requirement of an automobile tensile member (rapid manufacturing of sheet metal parts in the automobile industry) is ensured, and the mold is particularly suitable for parts with high quality standards such as automobile body outer covering parts, wing plates, side walls and the like;
the number of the outer covering parts of the automobile body of the die prepared from the composite material can reach more than 5000, and the requirements of trial production of samples and small-batch trial production can be met;
2. the metal-based polymer composite material is used for preparing the die, the surface of the die is not coated, the die has wear resistance and corrosion resistance, and the surface roughness can be polished into different grades from Ra6.4 to Ra0.8.
3. The epoxy resin has high adhesion force, and the epoxy resin has hydroxyl (-OH), ether (-CH-CH-0-) and extremely active epoxy (O) in the structure, so that the epoxy resin has high polarity, the epoxy resin molecule and an adjacent interface generate electromagnetic attraction, and a ring group can react with a free bond on a medium surface, particularly a metal surface to form a chemical bond, so that the adhesion force of the epoxy resin is particularly strong.
Based on the characteristics, if the surface of the die has defects, the surface can be reduced on the original basis for processing, if local molding modification is needed, secondary pouring can be performed locally, then finish machining is performed, and design change in the trial production process can be flexibly coped with;
4. the processing performance is excellent, the die is different from that of a traditional metal die, the alloy material shows the characteristic of plastics (easy turning) during processing, the cutter is not damaged, the processing time is greatly shortened, the processing cost is reduced, the processing time is 30% -50% of that of the traditional gray cast iron (FC30), and the plastic characteristic ensures that the processing does not vibrate, so that the high precision of the processing is ensured.
5. The epoxy resin, especially low molecular weight epoxy resin, has good fluidity at normal temperature due to small molecular weight, and is easy to be mixed with curing agent and other additives, thereby bringing great convenience to operation and ensuring smooth processing technology.
6. Low shrinkage, namely, the reaction of the modified epoxy resin and the curing agent is carried out through direct addition reaction, so that no by-product is generated and no air bubble is generated in the curing process, and the shrinkage rate is only one ten thousandth to five ten thousandth.
7. The special modified epoxy resin does not contain alkali salt, so that the special modified epoxy resin is not easy to deteriorate after long-term storage, the structure is not damaged, and the special modified epoxy resin has excellent chemical resistance and stability after being cured.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following description will clearly and completely describe the technical solutions of the present invention, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but 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.
Example one
A metal-based polymer material comprises the following components in parts by weight:
6-8 parts of Ti, 3-8 parts of 2000-mesh iron oxide powder, 1-3 parts of 1200-mesh iron oxide powder, 3-4 parts of 1600-mesh electrolytic iron powder, 1-5 parts of 1600-mesh reduced iron powder, 3-6 parts of 800-mesh reduced iron powder, 3-4 parts of 600-mesh carbon black, 4-7 parts of Cr, 3-7 parts of Mn, 5-7 parts of Mg, 1-5 parts of Zn, 1-5 parts of Wc, 1.5-3.5 parts of Al and 3-8.5 parts of ceramic micro powder.
5-10 parts of epoxy resin, 5-10 parts of modified epoxy resin, 6.6-12 parts of epoxy diluent, 0.2-0.5 part of dispersing agent, 0.2-0.5 part of anti-settling auxiliary agent, 1-2 parts of polymerization auxiliary agent and 2-5 parts of defoaming agent.
The modified epoxy resin is bisphenol A type epoxy resin (DGEBA type resin for short) with a chemical formula
The epoxy group reacts with free bonds on the surface of the medium (especially on the surface of the metal) to form chemical bonds.
Or, the epoxy resin can also be bisphenol F epoxy resin, also called bisphenol F diglycidyl ether, BPF for short, which is prepared by reacting phenol with formaldehyde under acid catalysis to generate bisphenol F, and then carrying out polycondensation reaction with epichlorohydrin in the presence of sodium hydroxide. This is a novel epoxy resin developed to reduce the viscosity of bisphenol A type epoxy resin itself and to have the same properties. The liquid bisphenol F type epoxy resin is generally obtained by reacting bisphenol F (diphenol methane) with epichlorohydrin under the action of NaOH.
The epoxy diluent can be n-butyl glycidyl ether BGE or allyl glycidyl ether AGE;
the dispersant can be selected from fatty alcohol and ethylene oxide condensate, and has the appearance (25 ℃): white flaky solid, pH (1% aqueous solution): 5-7, cloud point (5% NaCl solution): more than or equal to 94 ℃, water content: less than or equal to 1.0 percent, HLB value: 17-18;
the anti-settling auxiliary agent can be bentonite, fumed silica or lithium magnesium silicate;
the polymerization assistant can be selected from the following:
polysulfide: polythiols (suitable for polyamines, polyamides, tertiary amines)
Polycarboxylic acid: polymerized fatty acid (suitable anhydrides, tertiary amines)
Carbamate ester: urethane prepolymers (suitable polyamines, polyamides);
specifically, in the embodiment, the metal-based polymer material further includes 5-10 parts of a graphene resin solution; the graphene resin solution comprises the following components in parts by weight: 2-3 parts of graphene dispersion liquid and 90-100 parts of epoxy resin. Graphene is the thinnest but the hardest nano material in the world, and a single-layer graphene material is added, so that the strength and the heat conduction efficiency of the composite material can be greatly improved, and the anti-sedimentation effect of the material is improved.
Specifically, in this embodiment, the metal-based polymer material further includes 2 to 3 parts of a metal surface treatment agent. The metal surface treatment agent is used for removing impurities in the metal powder.
In the metal matrix polymer material of this embodiment, the powder content for promoting material intensity is more, including the metal powder: 6-8 parts of Ti, 3-8 parts of 2000-mesh iron oxide powder, 1-3 parts of 1200-mesh iron oxide powder, 3-4 parts of 1600-mesh electrolytic iron powder, 1-5 parts of 1600-mesh reduced iron powder, 3-6 parts of 800-mesh reduced iron powder, 3-4 parts of 600-mesh carbon black, 4-7 parts of Cr, 3-7 parts of Mn, 5-7 parts of Mg, 1-5 parts of Zn, 1-5 parts of Wc and 1.5-3.5 parts of Al; and 3-8.5 parts of ceramic micro powder and a single-layer graphene material, wherein the content of the metal powder and the ceramic micro powder is high, so that the composite material prepared by the high polymer material has high strength, high hardness and high modulus.
In the metal-based polymer material of the embodiment, the metal powder, the ceramic powder and the single-layer graphene material are added up to far exceed the components of the resin in parts; the resin component comprises 5-10 parts of epoxy resin, 5-10 parts of modified epoxy resin and a part of resin in the graphene resin solution, and the metal powder and the ceramic micro powder can still keep the metal-based high polymer material to have better fluidity under the condition of keeping large components.
3-8 parts of 2000-mesh iron oxide powder, 1-3 parts of 1200-mesh iron oxide powder, 3-4 parts of 1600-mesh electrolytic iron powder, 1-5 parts of 1600-mesh reduced iron powder, 3-6 parts of 800-mesh reduced iron powder and 3-4 parts of 600-mesh carbon black, and the powder with different meshes is graded and mixed for use, so that the prepared composite material and the mold can be more compact, and the structural strength and the structural stability of the composite material are improved.
Ti element: the internal structure of the composite material is compact, the grain force is refined, the strength of the composite material after curing is ensured, and the aging sensitivity and the cold brittleness are reduced.
Cr element: the strength and hardness of the composite material after curing improve the mechanical property of the composite material, so that the material has corrosion resistance and oxidation resistance;
mn element: strength and hardness of the composite material after curing;
mg element: in the composite material, the composite material has high specific strength and specific rigidity and good diamagnetism, so that the composite material has high shock absorption and cutting performance.
Zn element: improve the casting performance of the alloy, increase the fluidity of the alloy, refine crystal grains, cause solid solution strengthening and improve the mechanical performance.
Wc (tungsten carbide) element: the carbide is a binary compound formed by d transition elements, especially VIB and VIIB groups and iron series elements and carbon, and has the structural characteristics that carbon atoms are filled in tetrahedral holes of closely packed metal lattices, and the conductivity of the metal is not influenced.
Al element: a small amount of aluminum is added into the composite material, so that crystal grains can be refined, and the impact toughness is improved.
Carbon black: the heat and electric conductivity and the fluidity (lubricity) of the fluid are provided, and other metals provide respective characteristics, so that the performance is more excellent, and the toughness, the impact resistance, the compression resistance, the processability and the heat conductivity are obtained;
the ceramic micro powder is a light nonmetal multifunctional material, and the main component is SiO2And Al2O3Good dispersibility, good suspensibility, good chemical stability, good plasticity, high heat-resisting temperature, small density, and is a microsphere with high strength and hardnessThe hardness and the wear resistance of the metal-based polymer material of the embodiment can be enhanced;
the reduced iron powder has high purity, low impurity, good consistency, good compressibility and good formability, thus can provide high adhesive force, the epoxy resin has hydroxyl (-OH), ether (-CH-CH-0-) and extremely active epoxy group in the structure, so that the epoxy resin has very high polarity, the epoxy resin molecule and the adjacent interface generate electromagnetic attraction, the ring group can react with the free bond on the surface of the medium, especially the metal surface, to form chemical bond, and the reduced iron powder has very good electromagnetic attraction, and the two are very strong adhesive force after being superposed.
In the embodiment, the viscosity of the resin mixed solution is adjusted by the modified epoxy resin, the special modified epoxy resin does not contain alkali salt, so that the special modified epoxy resin is not suitable for being deteriorated after being stored for a long time, the structure is not damaged, so that the prepared composite material and the prepared mold are not sensitive to temperature, and the chemical resistance and the stability are excellent.
The dispersant is used for enabling the materials in the resin mixed liquid to be particularly uniform; the anti-settling auxiliary agent is suitable for preventing each substance in the composite material from settling after being homogenized; the polymerization assistant is suitable for polymerizing small molecular chains to form large molecular chains with higher epoxy equivalent; the defoaming agent eliminates the surface friction force of bubbles in the mixed solution, changes the surface polarity of the bubbles, is very smooth and convenient to float upwards, and achieves a compact solution;
the metal-based polymer of this example includes the following three preferred embodiments:
a first alternative embodiment: the metal-based high polymer material comprises 5 parts of epoxy resin, 5 parts of modified epoxy resin, 6.6 parts of epoxy diluent, 0.2 part of dispersing agent, 0.2 part of anti-settling auxiliary agent, 1 part of polymerization auxiliary agent and 2 parts of defoaming agent. 2 parts of a metal surface treating agent;
6 parts of Ti,3 parts of 2000-mesh iron oxide powder, 1 part of 1200-mesh iron oxide powder, 3 parts of 1600-mesh electrolytic iron powder, 1 part of 1600-mesh reduced iron powder, 3 parts of 800-mesh reduced iron powder, 3 parts of 600-mesh carbon black, 4 parts of Cr, 3 parts of Mn, 5 parts of Mg, 1 part of Zn, 1 part of Wc, 1.5 parts of Al and 3 parts of ceramic micro powder.
And 5 parts of graphene resin solution, wherein 2 parts of graphene dispersion solution is selected from the graphene resin solution and 90 parts of epoxy resin are matched for blending.
Second alternative embodiment: the metal-based high polymer material comprises 10 parts of epoxy resin, 10 parts of modified epoxy resin, 12 parts of epoxy diluent, 0.5 part of dispersing agent, 0.5 part of anti-settling auxiliary agent, 2 parts of polymerization auxiliary agent, 5 parts of defoaming agent and 3 parts of metal surface treating agent;
8 parts of Ti,8 parts of 2000-mesh iron oxide powder, 3 parts of 1200-mesh iron oxide powder, 4 parts of 1600-mesh electrolytic iron powder, 5 parts of 1600-mesh reduced iron powder, 6 parts of 800-mesh reduced iron powder, 4 parts of 600-mesh carbon black, 7 parts of Cr, 7 parts of Mn, 7 parts of Mg, 5 parts of Zn, 5 parts of Wc, 3.5 parts of Al and 8.5 parts of ceramic micro powder.
10 parts of a graphene resin solution; wherein, 2 parts of graphene dispersion liquid is selected from the graphene resin solution and is prepared by matching with 100 parts of epoxy resin.
A third alternative embodiment: the metal-based high polymer material comprises 6 parts of epoxy resin, 6 parts of modified epoxy resin, 8 parts of epoxy diluent, 0.3 part of dispersing agent, 0.3 part of anti-settling auxiliary agent, 1.5 parts of polymerization auxiliary agent, 3 parts of defoaming agent and 2.5 parts of metal surface treating agent;
7 parts of Ti, 4 parts of 2000-mesh iron oxide powder, 2 parts of 1200-mesh iron oxide powder, 4 parts of 1600-mesh electrolytic iron powder, 3 parts of 1600-mesh reduced iron powder, 5 parts of 800-mesh reduced iron powder, 3 parts of 600-mesh carbon black, 5 parts of Cr, 5 parts of Mn, 6 parts of Mg, 3 parts of Zn, 3 parts of Wc, 2 parts of Al and 5 parts of ceramic micro powder.
8 parts of a graphene resin solution; wherein, 3 parts of graphene dispersion liquid is selected from the graphene resin solution and is prepared by 100 parts of epoxy resin.
The polymer alloy material of the embodiment exists as the agent A in the composite material, and various component materials used in the composite material are prepared in advance, so that the metal-based polymer material disclosed by the invention is excellent in anti-settling performance, can keep good fluidity under the condition of high content of metal components, is easy to apply, and has excellent anti-settling performance for each component in the polymer material.
Example two
A preparation method of a metal-based polymer material comprises the following steps:
step S01, adding 5-10 parts of epoxy resin into a reaction kettle, heating to 90-100 ℃, and performing dispersion stirring in the heating process, wherein the dispersion stirring speed is 300-500 r/min;
step S02, after the temperature is raised to 100 ℃ and stabilized, adding 5-10 parts of modified epoxy resin, and continuously stirring for 20min after all the modified epoxy resin is added, wherein the stirring speed is 300-500/min; firstly, adjusting the concentration of a resin mixed solution by modifying epoxy resin;
step S03, adding 6.6-12 parts of epoxy diluent, and continuously stirring for 5min at a dispersion stirring speed of 300-500 r/min; adjusting the viscosity of the resin mixed solution by using an epoxy diluent;
step S04, adding 0.2-0.5 part of dispersing agent, and continuously stirring for 5min at a dispersing and stirring speed of 300-500 r/min; the material in the resin mixed liquid is particularly uniform through the dispersant;
step S05, adding 0.2-0.5 part of anti-settling auxiliary agent, and continuously stirring for 5min at a dispersion stirring speed of 300-500 r/min;
step S06, adding 1-2 parts of polymerization auxiliary agent, and continuously stirring for 5min at a dispersion stirring speed of 300-500 r/min; the epoxy equivalent of the resin mixed solution is improved by adding the polymerization auxiliary agent.
Step S07, adding 2-5 parts of defoaming agent, and continuously stirring for 5min at a dispersion stirring speed of 300-500 r/min; the defoaming agent is added to remove bubbles in the resin mixed liquid, so that the prepared resin mixed liquid material can be more compact, and the phenomenon of air holes in the subsequently prepared composite material and the mold is avoided.
Step S08, mixing 6-8 parts of Ti, 3-8 parts of 2000-mesh iron oxide powder, 1-3 parts of 1200-mesh iron oxide powder, 3-4 parts of 1600-mesh electrolytic iron powder, 1-5 parts of 1600-mesh reduced iron powder, 3-6 parts of 800-mesh reduced iron powder, 3-4 parts of 600-mesh carbon black, 4-7 parts of Cr, 3-7 parts of Mn, 5-7 parts of Mg, 1-5 parts of Zn, 1-5 parts of Wc, 1.5-3.5 parts of Al and 3-8.5 parts of ceramic micro powder to form metal mixed powder;
adding the metal mixed powder into the resin mixed liquid prepared in the step S07 until the powder is uniformly stirred to be fluid;
step S09 is to defoam the uniformly stirred fluid material to obtain a fluid metal-based polymer material.
Specifically, in step S08, the metal mixed powder is mixed with 2 to 3 parts of a metal surface treatment agent to be sprayed and stirred in advance to obtain pretreated metal mixed powder, the pretreated metal mixed powder is added into the resin mixed liquid to be stirred uniformly, a part of impurities are removed by treatment, and then the metal mixed powder is added, so that the material is more compact and uniform, and the subsequently prepared mold has higher strength and hardness.
Specifically, 5-10 parts of graphene resin solution is added in the adding process of the pretreated metal mixed powder; the graphene resin solution comprises the following components in parts by weight: 2-3 parts of graphene dispersion liquid and 90-100 parts of epoxy resin, and specifically, the graphene/epoxy resin composite material is prepared by selecting 2 parts of graphene dispersion liquid and 100 parts of epoxy resin.
EXAMPLE III
A composite material (metal-based polymer composite material) comprises the following components in parts by weight:
8-10 parts of metal-based polymer material and 1-2 parts of curing agent;
the metal-based polymer material is the metal-based polymer material in the first embodiment;
wherein the curing agent comprises 77-82 parts of polyether amine and 18-23 parts of alicyclic amine by weight;
there are three alternative examples of curing agents;
a first alternative embodiment: the curing agent comprises 77 parts of polyether amine and 23 parts of alicyclic amine by weight;
second alternative embodiment: the curing agent comprises 82 parts of polyether amine and 18 parts of alicyclic amine by weight;
a third alternative embodiment: the curing agent comprises 80 parts of polyether amine and 20 parts of alicyclic amine by weight;
the curing agent belongs to the existing product;
the polyether amine is a polymer with a main chain of a polyether structure and an active functional group at the tail end of the polymer as an amino group. The characteristics are as follows: pale yellow viscous liquid, density (g/mL at 25 ℃): 0.997, boiling point (. degree.C., 0.76 mmHg): 260, refractive index (n 20/D): 1.452, flash point (. degree. C.): 110, vapour pressure (mmHg,20 ℃): 0.75;
alicyclic amine (3-aminomethyl-3, 5, 5-trimethylcycloethylamine), melting point (. degree.C.) 10, boiling point (. degree.C.) 247, flash point (. degree.C.) 110, viscosity mPas (20 ℃ C.) 18(20 ℃ C.), toxicity LD50(mg/kg) rat is a colorless transparent liquid with slight ammonia odor through oral 1030;
the metal-based polymer material is used as an agent A, the curing agent is used as an agent B, the metal-based polymer material and the curing agent are mixed and stirred to form a fluid state, and then the fluid state is slowly cured into a metal-based polymer composite material, wherein the metal-based polymer composite material is as follows: 4,4' - (1-methylethylidene) biphenol and (chloromethyl) oxirane.
The principle of the addition reaction of epichlorohydrin (main component of resin) and amine curing agent is as follows:
the reaction principle of epichlorohydrin (main component of resin) and hydroxyl is as follows:
the polymerization reaction principle is as follows:
the metal-based polymer material is used as an agent A, the curing agent is used as an agent B, the metal-based polymer material and the curing agent are mixed and stirred to form a fluid state, and then the fluid state is slowly cured into a metal-based polymer composite material, wherein the metal-based polymer composite material is as follows: 100% of a polymer of 4,4' - (1-methylethylidene) biphenol and (chloromethyl) oxirane.
The performance specification of the metal-based polymer composite material in a fluid state after being uniformly mixed is shown in the following table;
| detecting items | Specification value |
| Viscosity/cps (LVT #3-60rpm/25 ℃ C.) | 8000～12000 |
| Gel time/min | 20～50 |
The mechanical property specification of a 4mm casting body of the metal-based polymer composite material after curing is shown in the following table;
| detecting items | Specification value | Test method |
| Tensile strength/MPa | 50～60 | IS0 527-2，GB/T 2567 |
| Elongation at break/%) | >1 | IS0 527-2，GB/T 2567 |
| Modulus of elasticity/MPa | 6500～7500 | IS0 527-2，GB/T 2567 |
| Flexural Strength/MPa | 95～105 | IS0 178，GB/T 2567 |
| Modulus of elasticity/MPa | 7000～8000 | IS0 178，GB/T 2567 |
| Hardness/shore D | >94 | GB/T 3854 |
The cured metal-based polymer composite material mainly comprises resin and metal powder, and the metal powder has high content. But not resin characteristics (the resin is soft and does not resist pressure, and the strength and hardness cannot be guaranteed).
The metal-based polymer composite material has the following three preferred embodiments:
a first alternative embodiment: the metal-based polymer composite is 10 parts of a metal-based polymer material and 1 part of a curing agent, and in this embodiment, the first is preferable. Specifically, the performance specifications of the metal-based polymer composite material in a fluid state after being uniformly stirred are shown in the following table;
| detecting items | Specification value |
| Viscosity/cps (LVT #3-60rpm/25 ℃ C.) | 12000 |
| Gel time/min | 40 |
The mechanical property specification of a 4mm casting body of the metal-based polymer composite material after curing is shown in the following table;
| detecting items | Specification value | Test method |
| Tensile strength/MPa | 55 | IS0 527-2，GB/T 2567 |
| Elongation at break/%) | 1.2 | IS0 527-2，GB/T 2567 |
| Modulus of elasticity/MPa | 7000 | IS0 527-2，GB/T 2567 |
| Flexural Strength/MPa | 105 | IS0 178，GB/T 2567 |
| Modulus of elasticity/MPa | 7900 | IS0 178，GB/T 2567 |
| Hardness/shore D | 95 | GB/T 3854 |
Second alternative embodiment: the metal-based polymer composite material is 9 parts of metal-based polymer material matched with 2 parts of curing agent; the performance specification of the metal-based polymer composite material in a fluid state after being uniformly mixed is shown in the following table;
| detecting items | Specification value |
| Viscosity/cps (LVT #3-60rpm/25 ℃ C.) | 8000 |
| Gel time/min | 30 |
The mechanical property specification of a 4mm casting body of the metal-based polymer composite material after curing is shown in the following table;
| detecting items | Specification value | Test method |
| Tensile strength/MPa | 50 | IS0 527-2，GB/T 2567 |
| Elongation at break/%) | 1.3 | IS0 527-2，GB/T 2567 |
| Modulus of elasticity/MPa | 6500 | IS0 527-2，GB/T 2567 |
| Flexural Strength/MPa | 98 | IS0 178，GB/T 2567 |
| Modulus of elasticity/MPa | 7500 | IS0 178，GB/T 2567 |
| Hardness/shore D | 96 | GB/T 3854 |
A third alternative embodiment: the metal-based polymer composite material is 8 parts of metal-based polymer material matched with 1 part of curing agent. Specifically, the performance specifications of the metal-based polymer composite material in a fluid state after being uniformly stirred are shown in the following table;
| detecting items | Specification value |
| Viscosity/cps (LVT #3-60rpm/25 ℃ C.) | 11000 |
| Gel time/min | 50 |
The mechanical property specification of a 4mm casting body of the metal-based polymer composite material after curing is shown in the following table;
| detecting items | Specification value | Test method |
| Tensile strength/MPa | 60 | IS0 527-2，GB/T 2567 |
| Elongation at break/%) | 1.1 | IS0 527-2，GB/T 2567 |
| Modulus of elasticity/MPa | 7500 | IS0 527-2，GB/T 2567 |
| Flexural Strength/MPa | 95 | IS0 178，GB/T 2567 |
| Modulus of elasticity/MPa | 7300 | IS0 178，GB/T 2567 |
| Hardness/shore D | 95.5 | GB/T 3854 |
Example four
A preparation method of a composite material (metal-based polymer composite material) comprises the following steps:
step P1, 1-2 parts of curing agent is taken and mixed with 9-10 parts of metal-based polymer material uniformly,
step P2, controlling the temperature at 20-35 ℃ for 3-5 hours to obtain a primarily cured polymer composite material;
and step P3, controlling the temperature of the preliminarily cured polymer composite material at 80-160 ℃ for 6-9 hours to obtain the finished product of the metal-based polymer composite material.
According to the preparation method, the composite material is cured at normal temperature, and then is placed in a high-temperature environment for post-curing after being cured at normal temperature, so that the metal-based polymer composite material prepared by the method is uniform in texture and high in strength and hardness.
EXAMPLE five
A mold, which is made of the metal-based polymer composite material in the third embodiment.
The mold has the following features:
1. the metal-based polymer composite material disclosed by the invention has more metal characteristics, pressure resistance, high hardness and high strength than resin characteristics, and because the resin is softer and cannot resist pressure, the strength and hardness cannot be guaranteed;
the mold, having a low coefficient of expansion and a high hardness, rockwell Hardness (HRC): 48-53, Shore D: is more than 94; the stamping die has the advantages that the requirements of trial production of sample parts and small-batch trial production can be met in the process of stamping the sheet metal parts by the die, the stamped parts are higher in precision, more products can be stamped, the number of the products can reach more than 5000, and the stamping die is particularly suitable for parts with high quality standards such as automobile body outer covering parts such as fenders.
2. The surface of the die has no coating and has abrasion resistance, the surface roughness can be polished into different grades from Ra6.4 to Ra0.8, and the surface finish can be determined according to the mesh number of the actually selected metal components;
the metal powder is wrapped by resin, can be isolated from water molecules, and has the purpose of corrosion prevention.
3. High adhesive force, see table 1, the viscosity of the fluid polymer composite is 8000-12000 cps; because the epoxy resin has a structure with hydroxyl (-OH), ether (-CH-CH-0-) and a very active epoxy group (O), the epoxy resin has high polarity, so that the epoxy resin molecules generate electromagnetic attraction with adjacent interfaces, and the ring group can react with free bonds on the surface of a medium, particularly on the surface of metal to form chemical bonds, so that the adhesive force of the epoxy resin is particularly strong.
Therefore, based on the characteristics, if the surface of the mold has defects, the surface can be reduced on the original basis for processing, if local modeling modification is needed, secondary pouring (pouring of the fluid-shaped polymer composite material) can be performed locally, and after curing, finish machining is performed, so that design change in the trial-manufacturing process can be flexibly coped with;
4. the processing performance is excellent, and the polymer composite material contains partial resin, so that the polymer composite material has the free-cutting characteristic of plastics. Different from the traditional metal die, the alloy material does not damage the cutter during processing, greatly shortens the processing time and reduces the processing cost, the processing time is 30-50% of the traditional gray cast iron (FC30), and the plastic characteristic of the alloy material ensures that the cutter is not vibrated during processing, thereby ensuring the high precision of processing.
5. The epoxy resin, especially low molecular weight epoxy resin, has good fluidity at normal temperature due to small molecular weight, and is easy to be mixed with curing agent and other additives, thereby bringing great convenience to operation and ensuring smooth processing technology.
After the metal-based polymer material and the curing agent are uniformly mixed, the polymer composite material still in the fluid state can better flow to each corner position in the pouring cavity due to the good fluid state (the viscosity is 8000-12000 cps), so that the manufactured die is higher in precision, and the precision of a stamped metal plate product is ensured.
6. Low shrinkage, namely, the reaction of the modified epoxy resin and the curing agent is carried out through direct addition reaction, so that no by-product is generated and no air bubble is generated in the curing process, and the shrinkage of the resin material is only one to five ten thousandths. The behavior in the mold is: the surface of the manufactured mould is smooth and clean, does not contain bubbles and has high surface smoothness, and after the mould after curing is recovered to normal temperature, the mould precision can be ensured due to small shrinkage rate, so that the product precision is ensured, and the product has high dimensional stability.
7. The special modified epoxy resin does not contain alkali salt, so that the special modified epoxy resin is not easy to deteriorate after long-term storage, the structure is not damaged, and the special modified epoxy resin has excellent chemical resistance and stability after being cured.
8. Anti-settling property, before preparing the metal-based composite material, the metal components in the metal-based polymer material, namely 2000-mesh iron oxide powder, 1200-mesh iron oxide powder, 1600-mesh electrolytic iron powder, 1600-mesh reduced iron powder, 800-mesh reduced iron powder and 600-mesh carbon black powder, the mesh numbers of the materials are different, and after the materials are mixed together, the compactness of the whole metal-based polymer material is higher (from the aspect of a micro-space structure, the space stacking property between the powders with different mesh numbers is better, the powders can be supported by each other higher, so that the metal powder settling is prevented), thereby leading the hardness and the strength of the manufactured mould to be higher.
After the metal-based high polymer material has the anti-settling performance, the metal-based high polymer material and the curing agent are uniformly stirred and mixed, and the texture of the mold formed by curing can be kept sufficiently uniform, so that the quality of the mold is ensured.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (5)
1. A preparation method of a metal-based high polymer material is characterized by comprising the following steps:
step S01, adding 5-10 parts of epoxy resin into a reaction kettle, heating to 90-100 ℃, and heating and stirring until the epoxy resin is uniformly dispersed;
step S02, after the temperature is raised to 100 ℃ and stabilized, adding 5-10 parts of modified epoxy resin, and stirring uniformly;
step S03, adding 6.6-12 parts of epoxy diluent until the mixture is uniformly stirred;
step S04, adding 0.2-0.5 part of dispersing agent until the mixture is uniformly stirred;
step S05, adding 0.2-0.5 part of anti-settling auxiliary agent until the mixture is uniformly stirred;
step S06, adding 1-2 parts of polymerization auxiliary agent, and stirring uniformly;
step S07, adding 2-5 parts of defoaming agent until the mixture is uniformly stirred;
step S08, mixing 6-8 parts of Ti, 3-8 parts of 2000-mesh iron oxide powder, 1-3 parts of 1200-mesh iron oxide powder, 3-4 parts of 1600-mesh electrolytic iron powder, 1-5 parts of 1600-mesh reduced iron powder, 3-6 parts of 800-mesh reduced iron powder, 3-4 parts of 600-mesh carbon black, 4-7 parts of Cr, 3-7 parts of Mn, 5-7 parts of Mg, 1-5 parts of Zn, 1-5 parts of Wc, 1.5-3.5 parts of Al and 3-8.5 parts of ceramic micro powder to form metal mixed powder;
adding the metal mixed powder into the resin mixed liquid prepared in the step S07 until the powder is uniformly stirred to be fluid;
step S09 is to defoam the uniformly stirred fluid material to obtain a fluid metal-based polymer material.
2. The method of claim 1, wherein in step S08, the metal mixed powder is mixed with 2-3 parts of metal surface treatment agent and then sprayed and stirred to obtain pre-treated metal mixed powder, and the pre-treated metal mixed powder is added into the resin mixture and stirred uniformly.
3. The method for preparing a metal-based polymer material according to claim 2, wherein 5 to 10 parts of graphene resin solution is added to the pretreated metal mixed powder during the addition process;
the graphene resin solution comprises the following components in parts by weight:
2 to 3 parts of a graphene dispersion, and
90-100 parts of epoxy resin.
4. The preparation method of the composite material is characterized by comprising the following steps:
step P1, 1-2 parts of curing agent is taken and matched with 9-10 parts of high polymer material until being mixed evenly,
step P2, controlling the temperature at 20-35 ℃ for 3-5 hours to obtain a primarily cured polymer composite material;
and P3, controlling the temperature of the preliminarily cured polymer composite material at 80-160 ℃ for 6-9 hours to obtain the finished polymer composite material.
5. A mold made of the polymer composite material prepared by the method for preparing a composite material according to claim 4.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112961635A (en) * | 2021-03-01 | 2021-06-15 | 上海英科心电图医疗产品有限公司 | Graphene-doped epoxy resin conductive adhesive and preparation method thereof |
| CN114316514A (en) * | 2021-11-06 | 2022-04-12 | 潍坊科技学院 | Epoxy gradient material and preparation method thereof |
| CN114605777A (en) * | 2022-04-03 | 2022-06-10 | 焦作市天益科技有限公司 | Epoxy resin-based composite material and method for reducing filler precipitation speed |
| CN114656748A (en) * | 2022-05-24 | 2022-06-24 | 天津金力研汽车工程技术有限公司 | Phenolic resin composition, preparation method thereof and application thereof in preparation of stamping die |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501866A (en) * | 2017-09-07 | 2017-12-22 | 苏州浩焱精密模具有限公司 | A kind of metal-resin composite die material and preparation method thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107501866A (en) * | 2017-09-07 | 2017-12-22 | 苏州浩焱精密模具有限公司 | A kind of metal-resin composite die material and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112961635A (en) * | 2021-03-01 | 2021-06-15 | 上海英科心电图医疗产品有限公司 | Graphene-doped epoxy resin conductive adhesive and preparation method thereof |
| CN112961635B (en) * | 2021-03-01 | 2022-09-02 | 上海英科心电图医疗产品有限公司 | Graphene-doped epoxy resin conductive adhesive and preparation method thereof |
| CN114316514A (en) * | 2021-11-06 | 2022-04-12 | 潍坊科技学院 | Epoxy gradient material and preparation method thereof |
| CN114605777A (en) * | 2022-04-03 | 2022-06-10 | 焦作市天益科技有限公司 | Epoxy resin-based composite material and method for reducing filler precipitation speed |
| CN114656748A (en) * | 2022-05-24 | 2022-06-24 | 天津金力研汽车工程技术有限公司 | Phenolic resin composition, preparation method thereof and application thereof in preparation of stamping die |
| CN114656748B (en) * | 2022-05-24 | 2022-07-26 | 天津金力研汽车工程技术有限公司 | Phenolic resin composition, preparation method thereof and application thereof in preparation of stamping die |
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