CN106584830A - Lightweight microarray high-molecular polymer/metal film composite material and preparation method thereof - Google Patents
Lightweight microarray high-molecular polymer/metal film composite material and preparation method thereof Download PDFInfo
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- CN106584830A CN106584830A CN201611169898.0A CN201611169898A CN106584830A CN 106584830 A CN106584830 A CN 106584830A CN 201611169898 A CN201611169898 A CN 201611169898A CN 106584830 A CN106584830 A CN 106584830A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2073—Multistep pretreatment
- C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
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- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The invention provides a lightweight microarray material; the density Rho of the lightweight microarray material is less than or equal to 1000mg/cm<3>; the lightweight microarray material has characteristics of light weight and high mechanical strength; the properties such as sound absorption, heat absorption and vibration absorption and the like are highly demanded in the fields of aviation, aerospace and building. The invention relates to a preparation method of a microarray high-molecular polymer/metal composite material. The method comprises the following two steps: (1) preparing a three-dimensional microarray polymer template of a designed structure by using a rapid forming technique; and (2) depositing a metal film on the surface of the three-dimensional microarray high-molecular polymer template. The microarray composite material prepared by the method has the properties such as low density, high strength, high temperature resistance, excellent optical property, excellent electrical property, excellent thermal property and abrasion resistance and the like, and is used as a multifunctional lightweight array material. The work is eager to provide valuable reference for lightweight engineering materials.
Description
Technical field
The invention belongs to lightweight technical field of function materials, and in particular to a kind of microarray high molecular polymer/metal foil
The preparation method of film composite material.
Background technology
Carry forward vigorously material and energy-saving and emission-reduction, Accelerate Conservation-minded Society Construction are realized in the lightweight equipped, minimizing
Key measure, is the developing direction of new century engineering science and technology.Greatly to ocean platform, big airframe and Motor train unit body, then arrive
Vehicle in daily life, or even little electronic radiation device etc., lightweight and multifunction become an important ring in its development.
Further mitigate weight on existing material and architecture basics and obtain more excellent combination property such as mechanical strength height, radiating
Performance is good, dynamic performance and vibration isolation, sound insulation property is adjustable etc. it is multi-functional be Materials challenge, and Materials become
Gesture.
Light porous material is the light multifunction material of a class excellent performance, all has in every field and is widely used.
Light porous material mainly has cellular material, foam metal material, lattice material at present, and these materials have low-density, high ratio
The excellent mechanical properties such as by force/specific stiffness, high tough, high-energy absorption, and it is damping, sound absorption, heat-insulated, sound insulation, electromagnetic shielding, resistance to
The special natures such as hot anti-corrosion, are the structure-function integration materials of excellent performance, and wherein lattice material is to develop rapidly in recent years
And the class novel materials for occurring, have function and structure dual function concurrently.
Microarray material is a kind of orderly ultra-light cellular material that a kind of model molecule dot matrix configuration is produced.Lattice material
The periodic structure material being made up of connecting rod unit between node and node.Its feature is carefully to see configuration to be two dimension
Or three-dimensional net rack system, the space in rack is not used for the implant for carrying.Not only saved using this design substantial amounts of
Quality, also improves specific stiffness and specific strength, and under equivalent weight, lattice material has more preferable than unordered micro-structure metal foam
Mechanical property, the space between rack is able to carry out oil storage, configuration battery etc. functionalization and requires:The porous feature of material meets
Carry out the requirement of heat convection, the unique stretch performance of rack causes which to actuate, brake and the research of damping vibration has greatly development
Space.Meanwhile, it also has the abilities such as good reduction noise, shielding electromagnetic radiation, shock resistance and collision energy-absorbing.
The preparation method of lattice structure material is closely related with the species of material, lattice structure and pore diameter range, directly
Affect the feasibility and technical and economic peculiarities of lattice structure materials application.The preparation of existing metal three-dimensional lattice structural material
Method mainly has cast to make method and assembling-welding.
A) cast makes method
The scheme of lattice material is prepared using melt film autofrettage technique：Slenderness ratio can be prepared using note membrane technology and be less than 5
Polymer architecture, makes polyester sacrificial mold of the monolayer with location hole with polyester, overlaps single layer structure by structural arrangement mode
Into space lattice structure, sand mo(u)ld is prepared by sacrificial mold of polymer, polymer melted is decomposed at high temperature, is formed a little in sand mo(u)ld
Battle array space, by the molten metal injection sand mo(u)ld of melting, removes sand mo(u)ld, so as to obtain metal lattice material after cooling.Using the technique,
The size of lattice structure cell element may diminish to several millimeters, and element diameter is then 1-2mm.
The shortcoming of casting includes that investment casting proposes very high requirement to the mobility of metal, and general material is difficult
To realize, the non-ferrous casting alloy with high fluidity, such as Cu-2Be wt%, Al-7Si-0.3Mg wt%, Cu- are only limitted to
4Si-14Zn wt%.Investment casting technological process is complicated, and high cost easily produces defect.ERG companies of the U.S. adopt fusible pattern
Casting has prepared high-quality and widely used high porosity fine-crystal spume aluminium alloy, but the material yield is little and expensive.
B) assembling-welding
A) punching net punching press
Punching net is, using more moulding material, can to adopt cut or punch forming at present research；Typically
Punching net species includes hexagon net and rhombus net.Wherein hexagon net can strike out tetrahedron core body, and rhombus net can be rushed
It is pressed into pyramid core body.
B) expanded metal lath punching press/folding
Expanded metal lath is made with former cleaved expansion of steel plate, and its body is light and bearing capacity is strong.It is a large amount of with punching net
Waste of materials is compared, and it is that in production process, wastage of material is few by former steel plate that its maximum advantage is made of expanded metals, thus cost
It is relatively low.
C) 3 D weaving
Lee etc. is prepared for monolayer tetrahedron and Kagome core bodys using three-dimensional silk weaving, and its main technological steps is such as
Under：Continuous screw silk thread is made first, and three one metal wires are turned round around together, and helix is obtained after plasticity torsional deformation.
Then helix is fixed using a framework.By fixed framework, helix is assembled into along the direction of Different Plane
Plane then according to the required number of plies and interlamellar spacing arrangement Kagemo planes, then is assembled into by Kagome planes by helix
Integrally, can be made into the core of single or multiple lift.
The shortcoming of assembling-welding includes that lattice structure material cost prepared by assembling-welding is high, and the material for obtaining
Expect for unordered porous, size it is larger；Hexagon, rhombus, the stability of tetrahedral structure and mechanical property are all not so good as diamond knot
Structure is strong.Additionally, the technical matters flow process is complicated, defect is easily produced.
The content of the invention
An object of the present invention is to provide a kind of preparation side of microarray high molecular polymer/metallic film composite
Method.Composite prepared by the present invention has a 3-D ordered multiporous structure, and porosity is high, and technological process is simple, with low-density,
The features such as high intensity.
The purpose of the present invention is achieved by the following technical solution：
1) three-dimensional microarray polymer template is prepared using rapid shaping technique：
A () selects rapid shaping technique, including：Stereolithograghy technology (SLA), digital optical processing (DLP), selection
Property laser sintered (SLS), fused deposition modeling (FDM).
B () selects mould material, i.e. high molecular polymer, including light-sensitive resin EX-200 types, light-sensitive resin
DXZ-100 types, light-sensitive resin DSM somos14120 types, acrylic resin, epoxy resin, polystyrene (PS),
Polyethylene terephthalate (PET), acrylonitrile-butadiene-styrene copolymer (ABS), Merlon (PC), poly- methyl-prop
E pioic acid methyl ester (PMMA), polyformaldehyde (POM), polrvinyl chloride (PVC), polypropylene (PP), polylactic acid (PLA), nylon, high fine wax
Deng.
C () selects the lattice structure of template, including：Simple cubic, body-centered cubic, face-centered cubic, simple six side, simple four
Side, body-centered tetragonal, six side of the R hearts, simple orthorhombic, the orthogonal O hearts, body-centered-orthorhomic, face-centered orthorhombic, simple tiltedly side, O heart monocline, simply
Three is oblique, diamond positive tetrahedron structure.
D () selects the lattice parameter of template, including：Template overall dimensions are long 2.5-3.0cm, width 1.5-2.0cm, height
0.7-1.2cm, is constituted in the cellular construction of lattice structure, the diameter 0.2-0.6mm of post, and the length of post is 0.6-2mm, and each is brilliant
The length of side of lattice unit is 3-5mm.
Comprehensive conditions above, prepares the template of unlike material, different dot matrix structure and parameters using rapid shaping technique.
2) in three-dimensional microarray polymer in-mold plate surface deposited metal thin film, obtain molded structure；
Its concrete operation step includes：
A () template surface is cleaned：It is cleaned by ultrasonic 15～30min in acetone, ultrasound embathes 15～30min in deionized water,
It is cleaned by ultrasonic 10～20min in ethanol, spontaneously dries.
The process of (b) template surface：Template will be such that plating process smoothly enters through roughening, neutralization, sensitization and the step of activation
OK.
C () obtains molded structure in three-dimensional microarray polymer in-mold plate surface deposited metal.
According to an aspect of the invention, there is provided a kind of microarray high molecular polymer/metallic film composite
Preparation method, it is characterised in that include：
A three-dimensional microarray polymer template) is prepared, and the three-dimensional with predetermined structure is prepared including using rapid shaping technique
Microarray polymer template；
B) in three-dimensional microarray polymer in-mold plate surface deposited metal thin film, molded structure is obtained,
Wherein,
Above-mentioned rapid shaping technique is from stereolithograghy technology (SLA), digital optical processing (DLP), selectivity
The one kind selected in laser sintered (SLS), fused deposition modeling (FDM)；
The technological parameter of Stereolithography technology (SLA) is：Filling scanning speed：200～500mm/s, sweep span：
0.1～0.5mm, light-dark cycle diameter：0.1～0.3mm, supports scanning speed：80～120mm/s, jumps across speed：300～
800mm/s, interlayer waiting time：1～5s, table feed speed：2～10mm/s, workbench immersion depth：5～10mm；
Digital light processes the technological parameter of molding (DLP)：Projected resolution 768 × 480, projection optical band 350～
450nm, 20～50 μm of slice thickness, cold curing, every layer hardening time 3～10s, each movement time of motor be 1～
5s；
The technological parameter of selective laser sintering (SLS) is：Laser power：10～50W, 60～180 DEG C of preheating temperature, cuts
Piece 0.1～2mm of thickness, 1000～2000mm/s of scanning speed；
The technological parameter of fused deposition modeling (FDM) is：Lift height：0.05～1.0mm, 100～400 DEG C of nozzle temperature.
A further aspect of the invention, the structure of above-mentioned three-dimensional microarray polymer template include from
At least one selected in lower structure：
Simple cubic, body-centered cubic, face-centered cubic, simple six side, simple tetragonal, body-centered tetragonal, six side of the R hearts, it is simple just
Friendship, the orthogonal O hearts, body-centered-orthorhomic, face-centered orthorhombic, simple tiltedly side, O heart monocline, simple triclinic, diamond positive tetrahedron structure.
A further aspect of the invention, the material of above-mentioned three-dimensional microarray polymer template is macromolecule
Polymer, including at least one selected from following material：
Light-sensitive resin EX-200 section bar material, light-sensitive resin DXZ-100 section bar material, light-sensitive resin DSM
Somos14120 section bar material, acrylic resin, epoxy resin, polystyrene (PS), polyethylene terephthalate
(PET), acrylonitrile-butadiene-styrene copolymer (ABS), Merlon (PC), polymethyl methacrylate (PMMA), poly-
Formaldehyde (POM), polrvinyl chloride (PVC), polypropylene (PP), polylactic acid (PLA), nylon, high fine wax.
A further aspect of the invention, the above-mentioned deposited metal on three-dimensional microarray polymer template are thin
The deposition process of the step of film is chemical plating and plating.
A further aspect of the invention, the material of above-mentioned metallic film are selected from following material
It is a kind of：
Single, mass percent purity is the nickel of 99.0%--99.9%, copper, aluminum, zinc, stannum, gold, silver, palladium or chromium；
Zinc-iron alloy, zinc-cobalt alloy, zinc titanium alloy, zinc chrome alloy, manganese alloy, admiro, signal bronze, cupro-nickel chromium
Alloy or AI alloy.
According to another aspect of the present invention, there is provided the microarray high molecular polymerization prepared with above-mentioned preparation method
Thing/metallic film composite.
A further aspect of the invention, the structure of above-mentioned microarray polymer/metal film composite material
In unit, the length of unit post is 0.5-2mm, a diameter of 0.2-0.6mm of unit post.
A further aspect of the invention, above-mentioned microarray high molecular polymer/metallic film composite
Density is less than 200mg/cm3, it is low-density light dot matrix material.
The microarray metal material that the present invention is provided is a kind of light dot matrix material of excellent performance, with prior art phase
Than advantages of the present invention includes：
1st, microarray stay in place form used in the present invention has order, designability strong.
2nd, Introduction To Stereolithography used in the present invention can prepare the microarray structural model of arbitrary structures, essence
Degree height and short preparation period.
3rd, chemically plating used in the present invention is good for the effect that reached of method of polymer/metal composite, film
Layer tack is good, and surface compact, coating are evenly distributed, and thicknesses of layers is controllable, and sedimentation rate is fast, reproducible.
4th, the microarray high molecular polymer/metallic film composite prepared by the present invention has 3-D ordered multiporous knot
Structure, the features such as with low-density, high intensity.
Description of the drawings
Fig. 1 is the flow chart for preparing microarray polymer/metal film composite material using the method for chemical plating.
Fig. 2 is the photo of diamond lattice structure template obtained in embodiment 1.
Fig. 3 is the photo of microarray polymer/metal nickel film composite material obtained in embodiment 2.
Specific embodiment
Below with reference to drawings and Examples, the present invention is described in further detail.
The preparation method of microarray high molecular polymer/metallic film composite according to an embodiment of the invention
Including the steps (as shown in Figure 1)：
1) preparation of three-dimensional microarray polymer template
A () selects rapid shaping technique, including the one kind selected from following technology：Stereolithograghy technology
(SLA), digital optical processing (DLP), selective laser sintering (SLS), fused deposition modeling (FDM).
In an embodiment according to the present invention, the technological parameter of Stereolithography technology (SLA) is：Filling scanning speed：
200～500mm/s, sweep span：0.1～0.5mm, light-dark cycle diameter：0.1～0.3mm, supports scanning speed：80～
120mm/s, jumps across speed：300～800mm/s, interlayer waiting time：1～5s, table feed speed：2～10mm/s, work
Make platform immersion depth：5～10mm.
In an embodiment according to the present invention, the technological parameter of digital light process molding (DLP) is：Projected resolution 768
× 480, project optical band 405nm, 30 μm of slice thickness, cold curing, every layer hardening time 6s, when motor is moved every time
Between be 2s.
In an embodiment according to the present invention, the technological parameter of selective laser sintering (SLS) is：Laser power：10～
50W, 60～180 DEG C of preheating temperature, 0.1～2mm of slice thickness, 1000～2000mm/s of scanning speed.
In an embodiment according to the present invention, the technological parameter of fused deposition modeling (FDM) is：Lift height：0.05～
1.0mm, 100～400 DEG C of nozzle temperature.
B () selects template moulding material, i.e. high molecular polymer, including the one kind selected from following material：Complex light
Quick resin EX-200 types, light-sensitive resin DXZ-100 types, light-sensitive resin DSM somos14120 types, esters of acrylic acid
Resin, epoxy resin, polystyrene (PS), polyethylene terephthalate (PET), acrylonitrile-butadiene-styrene copolymer
(ABS), Merlon (PC), polymethyl methacrylate (PMMA), polyformaldehyde (POM), polrvinyl chloride (PVC), polypropylene
(PP), polylactic acid (PLA), nylon, high fine wax etc..
C () selects the lattice structure of template, including the one kind selected from following structure：Simple cubic, body-centered cubic, face
The heart cube, simple six side, simple tetragonal, body-centered tetragonal, six side of the R hearts, simple orthorhombic, the orthogonal O hearts, body-centered-orthorhomic, face-centered orthorhombic,
Simple tiltedly side, O heart monocline, simple triclinic, diamond positive tetrahedron structure.
D () selects the lattice parameter of template；According to a particular embodiment of the invention, lattice parameter includes：Template entirety chi
It is very little for long 2.5-3.0cm, width 1.5-2.0cm, high 0.7-1.2cm, constitute in the cellular construction of lattice structure, constitute tetrahedral
The diameter 0.2-0.6mm of post, the length of post is 1-4mm, and the length of side of each lattice element is 3-5mm.
Comprehensive conditions above, prepares unlike material, different dot matrix structure and parameter using different rapid shaping techniques
Template.
2) in three-dimensional microarray polymer in-mold plate surface deposited metal thin film, obtain molded structure；
Its concrete operation step includes：
A () template surface is cleaned：It is cleaned by ultrasonic 15～30min in acetone, ultrasound embathes 15～30min in deionized water,
It is cleaned by ultrasonic 10～30min in ethanol, spontaneously dries.
The process of (b) template surface：Template will be such that plating process smoothly enters through roughening, neutralization, sensitization and the step of activation
OK.
Roughening process：Potassium permanganate 60g/L, sodium hydroxide 30g/L, temperature 60 C, time 15min.Neutralization technique：Oxalic acid
15g/L, temperature room temperature, till the time is cleared film.Sensitization technique：Stannous chloride (SnCl2.2H20) 15g/L, hydrochloric acid (HC1)
40ml/L, temperature room temperature, time 10min.Activating process：Stannous chloride 0.2g/L, hydrochloric acid (HC1) 5ml/L, temperature room temperature, when
Between 10min.
C () obtains molded structure using chemical plating and electric plating method in three-dimensional microarray template surface deposited metal.
During using chemical plating, pH=8.5 is adjusted with ammonia, reaction temperature is 60 DEG C, and electroless plating time is 5 minutes, is obtained
Molded structure.
Using during plating, electroplate liquid is first configured, the pH value of plating solution is then adjusted with ammonia, setting electroplating time is 2--10
Minute.
By obtained light porous microarray high molecular polymer/metallic film being compressed property of composite in embodiment
Can test.(5565 mechanics machines of INSTRUMENT MODEL INSTRON, translational speed is 5mm/min).
The concrete material quoted in following examples further illustrating advantages of the present invention and other details, but embodiment
Should not be considered as limitative to the invention with physical dimension and other conditions and details.
Embodiment 1
1) preparation of three-dimensional microarray polymer template
Gold is prepared using stereolithograghy technology (Stereo Lithography Appearance, SL or SLA)
The template of hard rock positive tetrahedron structure.
The technological parameter of Stereolithography technology (SLA) is：Filling scanning speed：300mm/s, sweep span：0.1mm,
Light-dark cycle diameter：0.2mm, supports scanning speed：100mm/s, jumps across speed：600mm/s, interlayer waiting time：5s, work
Platform feed speed：5mm/s, workbench immersion depth：6mm.
The mould material that Stereolithography technology (SLA) is adopted for：Light-sensitive resin EX-200 types, its main component is
Acrylic resin, as shown in Figure 2.
Diamond lattice structure template size is：A length of 28.94mm, a width of 19.68mm, a height of 10.05mm.Every post
A diameter of 0.6mm, the length of post is 2mm.
2) in three-dimensional microarray polymer in-mold plate surface deposited metal nickel thin film, obtain molded structure；
Its concrete operation step includes：
(201) point template is put in the solution containing potassium permanganate and sodium hydroxide, carries out surface coarsening 10 minutes, obtain
First intermediate die plate.
The solution containing potassium permanganate and sodium hydroxide both compositions of the 1L is potassium permanganate and 30g with 60g
Sodium hydroxide, deionized water are formulated into 1L.
(202) the first intermediate die plate is put in the hydrochloric activating solution with both compositions of stannous chloride, is activated
Process 20 minutes, obtain the second intermediate die plate.
The activating solution system of the hydrochloric and stannous chloride of the 1L with the stannous chloride and mass percent concentration of 15g is
The hydrochloric acid of 37.5% 40ml, deionized water are formulated into 1L.
(203) the second intermediate die plate is put in chemical nickel-plating solution carries out chemical plating, adjusts pH=8.5 with ammonia, instead
Temperature is answered for 60 DEG C, electroless plating time is 5 minutes, and nickel plating molded body is obtained.
It is the NiSO with 35g in the chemical nickel-plating solution of the 1L4·6H2O (six hydration nickel sulfate), 35g's
NaH2PO2·H2O (a waterside sodium phosphate), the C of 25g3H5NaO3(sodium lactate), the NH of 30g4Cl (ammonium chloride), analyzes pure 10ml
(HOC2H4)3N (triethanolamine), deionized water is formulated into 1L.
Obtained light porous microarray metal-polymer polymer/metal nickel film composite material in embodiment 1 is entered
Row compression performance tests (5565 mechanics machines of INSTRUMENT MODEL INSTRON, translational speed is 5mm/min).Measure maximum compression
Stress is 1.3MPa.
Embodiment 2
1) preparation of three-dimensional microarray polymer template
Diamond tetrahedron lattice structure mould is prepared using fused deposition modeling (Fused Deposition Modeling, FDM)
Plate.
In the present invention, the technological parameter of fused deposition modeling (FDM) is：Lift height：0.05～1.0mm, nozzle temperature
100～400 DEG C.
The mould material that fused deposition modeling (FDM) is adopted for：Light-sensitive resin EX-200 types, its main component are acrylic acid
Resin.
Diamond lattice structure template size is：A length of 28.94mm, a width of 19.68mm, a height of 10.05mm.Every post
A diameter of 0.3mm, the length of post is 1mm.
2) in three-dimensional microarray polymer in-mold plate surface deposited metal nickel thin film, molded structure is obtained, as shown in Figure 3.
Its concrete operation step is same as Example 1.
Embodiment 3
1) preparation of three-dimensional microarray polymer template
Diamond positive tetrahedron is prepared using selective laser sintering (Selective Laser Sintering, SLS)
The template of structure.
The technological parameter of selective laser sintering (SLS) is：Laser power：30W, 100 DEG C of preheating temperature, slice thickness
0.2mm, scanning speed 1800mm/s.
The mould material that selective laser sintering (SLS) is adopted for：Light-sensitive resin DSM somos14120 types, its master
Composition is wanted to be epoxy acrylic resin.
Diamond lattice structure template size is：A length of 28.94mm, a width of 19.68mm, a height of 10.05mm.Every post
A diameter of 0.6mm, the length of post is 2mm.
2) in three-dimensional microarray polymer in-mold plate surface deposited metal Copper thin film, obtain molded structure；
Its concrete operation step includes：
(201) point template is put in the solution containing two kinds of compositions of potassium permanganate and sodium hydroxide, carries out surface coarsening
10 minutes, obtain the first intermediate die plate.
Described solution the system potassium permanganate and 30g of 60g containing potassium permanganate and sodium hydroxide both compositions
Sodium hydroxide, deionized water are formulated into 1L.
(202) the first intermediate die plate is put in the hydrochloric activating solution with both compositions of stannous chloride, is lived
Change and process 20 minutes, obtain the second intermediate die plate.
The activating solution of the 1L hydrochloric and stannous chloride both compositions needs the stannous chloride and quality percentage of 15g
Specific concentration is the hydrochloric acid of 37.5% 40ml, and deionized water is formulated into 1L.
(203) the second intermediate die plate is put in chemical copper plating solution carries out chemical plating, adjusts pH=8.5 with ammonia, instead
Temperature is answered for 60 DEG C, electroless plating time is 5 minutes, and polymer/metal Copper thin film composite material molded body is obtained.
Need the copper sulfate of 6g in the chemical copper plating solution of the 1L, 20g potassium hydrogen tartrates, 18g sodium hydroxide, 0.2g's
2- sulfurio benzo thiazoles and 3g ammonium chloride and 5mL Biformyls, deionized water are formulated into 1L.
Obtained light porous microarray metal-polymer polymer/metal Copper thin film composite in embodiment 3 is entered
Row compression performance tests (5565 mechanics machines of INSTRUMENT MODEL INSTRON, translational speed is 5mm/min).Measure maximum compression
Stress is 1.1MPa.
Embodiment 4
1) preparation of three-dimensional microarray polymer template
Diamond positive tetrahedron structure is prepared using digital optical processing (Digital Light Processing, DLP)
Template.
Digital light processes the technological parameter of molding (DLP)：Projected resolution 768 × 480, projects optical band 405nm, cuts
30 μm of piece thickness, cold curing, every layer hardening time 6s, each movement time of motor be 2s.
Digital light process molding (DLP) mould material that adopts for：Light-sensitive resin DXZ-100 types, its main component
For methacrylic resin.
Diamond lattice structure template size is：A length of 28.03mm, a width of 18.94mm, a height of 9.54mm.Every post
A diameter of 0.3mm, the length of post is 1mm.This structure has very high structural stability, the physics with elasticity and anti-destructive
Stability.
2) in three-dimensional microarray polymer in-mold plate surface deposited metal Copper thin film, obtain molded structure；
Its concrete operation step is same as Example 3.
Embodiment 5
1) preparation of three-dimensional microarray polymer template
Diamond positive tetrahedron is prepared using selective laser sintering (Selective Laser Sintering, SLS)
The template of structure.
The technological parameter of selective laser sintering (SLS) is：Laser power：30W, 100 DEG C of preheating temperature, slice thickness
0.2mm, scanning speed 1800mm/s.
The mould material that selective laser sintering (SLS) is adopted for：Light-sensitive resin EX-200 types, its main component is
Acrylic resin.
Diamond lattice structure template size is：A length of 28.94mm, a width of 19.68mm, a height of 10.05mm.Every post
A diameter of 0.6mm, the length of post is 2mm.
2) in three-dimensional microarray polymer template electroplating surface zinc-nickel membrane material, obtain molded structure；
Its concrete operation step includes：
(201) point template is put in the solution containing two kinds of compositions of potassium permanganate and sodium hydroxide, carries out surface coarsening
10 minutes, obtain the first intermediate die plate.
The solution containing two kinds of compositions of potassium permanganate and sodium hydroxide for preparing 1L needs the potassium permanganate and 30g of 60g
Sodium hydroxide, deionized water is formulated into 1L.
(202) the first intermediate die plate is put in the hydrochloric activating solution with both compositions of stannous chloride, is activated
Process 20 minutes, obtain the second intermediate die plate.
The activating solution of two kinds of compositions of the hydrochloric and stannous chloride for preparing 1L needs the stannous chloride and quality of 15g
Percent concentration is the hydrochloric acid of 37.5% 40ml, and deionized water is formulated into 1L.
(203) the second intermediate die plate being discharged in zinc-plated nickel solution, pH=4.5 being adjusted with ammonia, electroplating time is 3 points
Clock, is obtained molded structure of the zinc-nickel film thickness for 500nm.
Need the Nickel dichloride. of 100g in the electrogalvanizing nickel solution of the 1L, the zinc chloride of 80g, the potassium chloride of 150g, 50g's
Ammonium chloride, the sodium lauryl sulphate of the boric acid and 0.06g of 20g, deionized water are formulated into 1L.
Obtained light porous microarray metal-polymer polymer/zinc-nickel film composite material in embodiment 5 is carried out
Compression performance tests (5565 mechanics machines of INSTRUMENT MODEL INSTRON, translational speed is 5mm/min).Measuring maximum compression should
Power is 1.05MPa.
Embodiment 6
1) preparation of three-dimensional microarray polymer template
Gold is prepared using stereolithograghy technology (Stereo Lithography Appearance, SL or SLA)
The template of hard rock positive tetrahedron structure.
The technological parameter of Stereolithography technology (SLA) is：Filling scanning speed：300mm/s, sweep span：0.1mm,
Light-dark cycle diameter：0.2mm, supports scanning speed：100mm/s, jumps across speed：600mm/s, interlayer waiting time：5s, work
Platform feed speed：5mm/s, workbench immersion depth：6mm.
The mould material that Stereolithography technology (SLA) is adopted for：Nylon.
Diamond lattice structure template size is：A length of 28.94mm, a width of 19.68mm, a height of 10.05mm.Every post
A diameter of 0.6mm, the length of post is 2mm.
2) the electroplating copper tin alloy membrane material on three-dimensional microarray polymer template, obtains molded structure；
Its concrete operation step includes：
(201) point template is put in the solution containing two kinds of compositions of potassium permanganate and sodium hydroxide, carries out surface coarsening
10 minutes, obtain the first intermediate die plate.
The solution containing two kinds of compositions of potassium permanganate and sodium hydroxide for preparing 1L needs the potassium permanganate and 30g of 60g
Sodium hydroxide, deionized water is formulated into 1L.
(202) the first intermediate die plate is put in the hydrochloric activating solution with both compositions of stannous chloride, is activated
Process 20 minutes, obtain the second intermediate die plate.
The activating solution for preparing 1L hydrochloric and stannous chloride both compositions needs the stannous chloride and quality of 15g
Percent concentration is the hydrochloric acid of 37.5% 40ml, and deionized water is formulated into 1L.
(203) the second intermediate die plate is put in electro-coppering solution of tin and is electroplated, pH=6.2, plating are adjusted with ammonia
Time is 3 minutes, and molded body of the corronil film thickness for 500nm is obtained.
Need the STANNOUS SULPHATE CRYSTALLINE of 22g in the electro-coppering solution of tin of the 1L, the copper sulfate of 25g, the ferric ammonium citrate of 100g,
50g ammonium sulfate, deionized water are formulated into 1L.
Obtained light porous microarray metal-polymer polymer/copper and tin film composite material in embodiment 6 is carried out
Compression performance tests (5565 mechanics machines of INSTRUMENT MODEL INSTRON, translational speed is 5mm/min).Measuring maximum compression should
Power is 1.2MPa.
Claims (8)
1. a kind of preparation method of microarray high molecular polymer/metallic film composite, it is characterised in that include：
A three-dimensional microarray polymer template) is prepared, and the three-dimensional microdot with predetermined structure is prepared including using rapid shaping technique
Battle array polymer template；
B) in three-dimensional microarray polymer in-mold plate surface deposited metal thin film, molded structure is obtained,
Wherein,
Described rapid shaping technique is from stereolithograghy technology (SLA), digital optical processing (DLP), selective laser
The one kind selected in sintering (SLS), fused deposition modeling (FDM)；
The technological parameter of Stereolithography technology (SLA) is：Filling scanning speed：200～500mm/s, sweep span：0.1～
0.5mm, light-dark cycle diameter：0.1～0.3mm, supports scanning speed：80～120mm/s, jumps across speed：300～800mm/s,
The interlayer waiting time：1～5s, table feed speed：2～10mm/s, workbench immersion depth：5～10mm；
Digital light processes the technological parameter of molding (DLP)：Projected resolution 768 × 480, projects 350～450nm of optical band,
20～50 μm of slice thickness, cold curing, every layer hardening time 3～10s, each movement time of motor be 1～5s；
The technological parameter of selective laser sintering (SLS) is：Laser power：10～50W, 60～180 DEG C of preheating temperature, slice thick
Degree 0.1～2mm, 1000～2000mm/s of scanning speed；
The technological parameter of fused deposition modeling (FDM) is：Lift height：0.05～1.0mm, 100～400 DEG C of nozzle temperature.
2. preparation method according to claim 1, it is characterised in that the structure of described three-dimensional microarray polymer template
Including at least one selected from following structure：
Simple cubic, body-centered cubic, face-centered cubic, simple six side, simple tetragonal, body-centered tetragonal, six side of the R hearts, simple orthorhombic, O
The heart is orthogonal, body-centered-orthorhomic, face-centered orthorhombic, simple tiltedly side, O heart monocline, simple triclinic, diamond positive tetrahedron structure.
3. preparation method according to claim 1, it is characterised in that the material of described three-dimensional microarray polymer template
For high molecular polymer, including at least one selected from following material：
Light-sensitive resin EX-200 section bar material, light-sensitive resin DXZ-100 section bar material, light-sensitive resin DSM
Somos14120 section bar material, acrylic resin, epoxy resin, polystyrene (PS), polyethylene terephthalate
(PET), acrylonitrile-butadiene-styrene copolymer (ABS), Merlon (PC), polymethyl methacrylate (PMMA), poly-
Formaldehyde (POM), polrvinyl chloride (PVC), polypropylene (PP), polylactic acid (PLA), nylon, high fine wax.
4. preparation method according to claim 1, it is characterised in that described sinks on three-dimensional microarray polymer template
The deposition process of the step of product metallic film is chemical plating and plating.
5. preparation method according to claim 1, it is characterised in that the material of described metallic film is from following material
In one kind for selecting：
Single, mass percent purity is the nickel of 99.0%--99.9%, copper, aluminum, zinc, stannum, gold, silver, palladium or chromium；
Zinc-iron alloy, zinc-cobalt alloy, zinc titanium alloy, zinc chrome alloy, manganese alloy, admiro, signal bronze, cupro-nickel evanohm
Or AI alloy.
6. with the microarray high molecular polymer/metallic film composite wood prepared according to the preparation method of one of claim 1-5
Material.
7. microarray high molecular polymer/metallic film composite according to claim 6, it is characterised in that described micro-
In the construction unit of dot matrix polymer/metal film composite material, the length of unit post is 0.5-2mm, unit post it is a diameter of
0.2-0.6mm。
8. microarray high molecular polymer/metallic film composite according to claim 6, it is characterised in that described
Microarray high molecular polymer/metallic film composite density is less than 200mg/cm3, it is low-density light dot matrix material.
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| CN109722654A (en) * | 2017-10-31 | 2019-05-07 | 北京航空航天大学 | The method that ultralight metal hollow pipe lattice material is constructed using high-molecular lattice template |
| CN108038293A (en) * | 2017-12-06 | 2018-05-15 | 首都航天机械公司 | A kind of light multifunction lattice structure and its laser gain material manufacture method |
| CN108372302A (en) * | 2018-01-07 | 2018-08-07 | 北京工业大学 | A method of preparing high specific strength using 3D printing, high resiliency deforms lattice structure copper alloy |
| CN109440089B (en) * | 2018-10-26 | 2021-02-02 | 东南大学 | Metal foil type strain gauge design and manufacturing method based on hybrid 3D printing technology |
| CN109440089A (en) * | 2018-10-26 | 2019-03-08 | 东南大学 | Metal foil stain gauge design and manufacturing method based on mixing 3D printing technique |
| CN109321770A (en) * | 2018-11-21 | 2019-02-12 | 上海交通大学 | A kind of nanometer of enhancing porous material and preparation method thereof |
| CN110039773B (en) * | 2019-05-08 | 2020-07-28 | 清华大学 | Three-dimensional printer with composite process and printing method thereof |
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| CN111468714A (en) * | 2020-05-14 | 2020-07-31 | 苏州大学 | Metal micro-lattice structure material and preparation method thereof |
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| CN114542208A (en) * | 2022-02-23 | 2022-05-27 | 中国航发沈阳发动机研究所 | Dot-matrix containing casing of aircraft engine |
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