Nothing Special   »   [go: up one dir, main page]

CN103980592B - A kind of high filler loading capacity micro nano powder/polymer composites for 3D printing and preparation method thereof and goods - Google Patents

A kind of high filler loading capacity micro nano powder/polymer composites for 3D printing and preparation method thereof and goods Download PDF

Info

Publication number
CN103980592B
CN103980592B CN201410183157.2A CN201410183157A CN103980592B CN 103980592 B CN103980592 B CN 103980592B CN 201410183157 A CN201410183157 A CN 201410183157A CN 103980592 B CN103980592 B CN 103980592B
Authority
CN
China
Prior art keywords
micro nano
nano powder
powder
goods
loading capacity
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201410183157.2A
Other languages
Chinese (zh)
Other versions
CN103980592A (en
Inventor
沈衡
朱唐
郭靖
赵宁
徐坚
孙文华
董金勇
李春成
符文鑫
林学春
马永梅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Chemistry CAS
Original Assignee
Institute of Chemistry CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Chemistry CAS filed Critical Institute of Chemistry CAS
Priority to CN201410183157.2A priority Critical patent/CN103980592B/en
Publication of CN103980592A publication Critical patent/CN103980592A/en
Priority to US15/507,670 priority patent/US11299569B2/en
Priority to PCT/CN2015/077360 priority patent/WO2015165363A1/en
Application granted granted Critical
Publication of CN103980592B publication Critical patent/CN103980592B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B29B2009/125—Micropellets, microgranules, microparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92009—Measured parameter
    • B29C2948/92209—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92714—Degree of crosslinking, solidification, crystallinity or homogeneity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92904—Die; Nozzle zone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/06—Crosslinking by radiation

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Toxicology (AREA)
  • Manufacturing & Machinery (AREA)
  • Optics & Photonics (AREA)
  • Dispersion Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Thermal Sciences (AREA)

Abstract

The present invention relates to a kind of high filler loading capacity micro nano powder/polymer composites for 3D printing and preparation method thereof and goods, the raw material of described material comprises: polymkeric substance 10-30 weight part, micro nano powder 90-70 weight part, irradiation sensitizing agent 0.05-0.2 weight part, oxidation inhibitor 0.01-0.02 weight part.The present invention uses micro nano powder as material of main part, fluoropolymer resin is as caking agent, the mode printing shaping printed by 3D, add irradiation sensitizing agent simultaneously, through electron beam irradiation post-consumer polymer resin formation three-dimensional crosslinked network, improve resin-bonded after intensity, thermotolerance and chemical resistance.The micro nano powder of high filler loading capacity imparts the mechanical property of formed material excellence.In addition, the environment used according to product and the change of demand, change the kind of micro nano powder, can obtain the material with specific functionality, as the electroconductibility of excellence, and thermal conductivity, flame retardant resistance and shock resistance etc.

Description

A kind of high filler loading capacity micro nano powder/polymer composites for 3D printing and preparation method thereof and goods
Technical field
The present invention relates to a kind of material for 3D printing and preparation method thereof and goods, be specifically related to a kind of high filler loading capacity micro nano powder/polymer composites for 3D printing and preparation method thereof and goods.
Background technology
It is a kind of emerging rapid shaping technique that 3D prints, by microcomputer modelling, three-dimensional model program is set, utilize laser sintered, the mode such as heating and melting, ultra-violet curing by materials such as metal, ceramic powder or polymkeric substance, controlled by computer digit software program, successively pile up molding bonded, thus produce entity products.3D prints in simple terms, can be regarded as the superposition spatially of 2D printing technique.Use the material such as pressed powder or polymer melt as printing " ink ", designed by microcomputer modelling, the precision of precisely control product and size.This printing technique is compared to traditional forming technique, do not need complicated mould and technique, equipment is small and exquisite, program is by computer control, easy and simple to handle, and the concern be thus subject to gets more and more, wide application space has been opened up gradually in fields such as biology, medical science, building, aviations, especially short run is applicable to, personalized, baroque hollow part.
It is nylon, ABS, polycarbonate and PPSU etc. that 3D used at present prints the most frequently used polymer materials, needs comparatively high temps during these forming materials, and not only shaping speed is slow, and finished product is poor at the aspect of performance such as intensity, toughness.By contrast, the exploitation of other 3D printed material is very rare, and this practicality also making 3D print, universality are restricted.Therefore, it is very important for developing new 3D printed material to make up the deficiency of above material.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, a kind of high filler loading capacity micro nano powder/polymer composites printed for 3D is provided.
Another object of the present invention is the preparation method providing a kind of above-mentioned matrix material.
Another object of the present invention is to provide a kind of by the above-mentioned goods prepared for the high filler loading capacity micro nano powder/polymer composites of 3D printing, and described goods have high strength and specific function.
4th object of the present invention is the preparation method providing a kind of said products.
5th object of the present invention is the purposes providing a kind of above-mentioned matrix material.
For achieving the above object, the present invention adopts following technical scheme:
For high filler loading capacity micro nano powder/polymer composites that 3D prints, described material is using micro nano powder as body material, and fluoropolymer resin is as binding agent, and the raw material of described material and content (weight part) thereof comprising:
Micro nano powder 90-70 part,
Fluoropolymer resin 10-30 part,
Irradiation sensitizing agent 0.05-0.2 part.
According to the present invention, described matrix material is obtained by the method for the mixing and screw extrusion press extruding pelletization that comprise raw material.
Micro nano powder of the present invention refers to the particulate matter of particle diameter between 1 nanometer and 100 microns.Preferably, described micro nano powder is inorganic micro nano powder; More preferably, described inorganic micro nano powder is selected from one or more in metal simple-substance powder, metal-oxide powder, non-metal simple-substance powder, silver halide powder, carbonate powder, phosphate powder, silicate powder and clay class powder.Preferably, the particle diameter of described micro nano powder is between 50nm and 10 μm.
Preferably, described micro nano powder, is through the micro nano powder of surface modifying agent.
Preferably, described surface-modifying agent be selected from Dopamine HCL and silane coupling agent one or more, described silane coupling agent is such as KH550, KH560, KH570, KH792 or DL602.
According to the present invention, described fluoropolymer resin is thermoplastic resin.Described thermoplastic resin is selected from polyolefine (PE, PP, PVC, PS), polymeric amide (PA), polycarbonate (PC), polyoxymethylene (POM), ethylene-vinyl acetate copolymer (EVA), polyester (PET, PBT, PCL, PLA), acrylonitrile-butadiene-styrene copolymer (ABS), styrene-butadiene-styrene block copolymer (SBS), styrene isoprene styrene block copolymer (SIS) (SIS), transparent butadiene-styrene impact resin (K resin), one or more in polyacrylic ester.
According to the present invention, the melting index of selected fluoropolymer resin is at least greater than 10.
According to the present invention, described radiosensitizer be selected from triallylcyanurate, cyanacrylate, three methylpropenyl isocyanic ester, trimethylolpropane trimethacrylate, Viscoat 295, trimesic acid triallyl, diallyl isocyanic ester, m-phthalic acid two propylene, bismaleimides, dimethacrylate triethyleneglycol ester, dimethacrylate glycol ether ester one or more.
According to the present invention, also comprise in described raw material:
Oxidation inhibitor 0.01-0.02 part.
According to the present invention, described oxidation inhibitor is Hinered phenols antioxidant and/or phosphorous acid esters auxiliary antioxidant.Preferably, antioxidant 1010 is selected from: four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Oxidation inhibitor 1096:IRGANOXB-1096; Primary antioxidant 1098:(N, N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine) and phosphite ester kind antioxidant interworking thing; And irgasfos 168: one or more in three [2,4-di-tert-butyl-phenyl] phosphorous acid ester.
According to the present invention, the raw material of described material and content (weight part) thereof are:
Micro nano powder 90-70 part,
Fluoropolymer resin 10-30 part,
Irradiation sensitizing agent 0.05-0.2 part,
Oxidation inhibitor 0.01-0.02 part.
The present invention also provides following technical scheme:
The preparation method of above-mentioned high filler loading capacity micro nano powder/polymer composites for 3D printing, it comprises the mixing of raw material and the step of screw extrusion press extruding pelletization.
According to the present invention, described method specifically comprises:
1) modification of micro nano powder;
2) mixing of each raw material;
3) screw extrusion press extruding pelletization.
According to the present invention, above-mentioned steps 1) be specially: the described surface-modifying agent of described micro nano powder 5-20 part of 100 weight parts is carried out surface modification in the solution.
According to the present invention, described step 2) be specially: by the fluoropolymer resin of 10-30 weight part, the modified micro nano powder of 90-70 part, the irradiation sensitizing agent of 0.05-0.2 part, the oxidation inhibitor of 0.01-0.02 part at room temperature mixes, sending into length-to-diameter ratio is extruding pelletization in the twin screw extruder of 36, forcing machine rotating speed is 20-100r/min, and the temperature range that forcing machine is each section is: feeding section 150-170 DEG C, melt zone 190-200 DEG C, mixing section 190-200 DEG C, exhaust section 170-190 DEG C, homogenizing zone 160-180 DEG C.
The present invention also provides following technical scheme:
A kind of goods, it prints obtained by the above-mentioned high filler loading capacity micro nano powder/polymer composites for 3D printing by 3D.
The preparation method of said products, comprises the step printed by 3D by the above-mentioned high filler loading capacity micro nano powder/polymer composites being used for 3D printing.
According to the present invention, described step specifically comprises:
The pellet of described matrix material is added the shower nozzle of 3D printer, by heat fused in shower nozzle, shower nozzle is along part section profile and fill orbiting motion, the material of fusing is extruded simultaneously, extrude rear rapid solidification under the control of the computer, and use electron beam to carry out irradiation, make crosslink material, layer by layer stack shaping.
According to the present invention, the parameter of described irradiation specifically: electron accelerator energy is 0.3-5MeV, power 50-150KW, and irradiation dose is 5-20KGy.
A purposes for above-mentioned high filler loading capacity micro nano powder/polymer composites for 3D printing, it prints for 3D.
The feature that the present invention gives prominence to is:
1, the micro nano powder in matrix material of the present invention has carried out chemical modification, effectively enhances the interaction of powder and fluoropolymer resin.
2, matrix material of the present invention makes fluoropolymer resin form three-dimensional crosslinked network by electronic irradiation technique in preparation process, improves thermostability and the chemical resistance of resin, and then improves the performance of described matrix material.
3, matrix material of the present invention has above-mentioned many excellent properties, be particularly suitable for as 3D printing material, obtained goods have excellent hardness, dimensional stability, thermotolerance, according to the difference of filling micro nano powder, electroconductibility can be had, thermal conductivity, flame retardant resistance simultaneously, wear resistance, the specific functions such as barrier properties for gases.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should be interpreted as scope of the present invention is only limitted to following example.When not departing from aforesaid method thought of the present invention, the various replacement made according to ordinary skill knowledge and customary means or change, all should be within the scope of the present invention.
Embodiment 1
A kind of high filler loading capacity micro nano powder/polymer composites printed for 3D
1) by the 500nmAg powder of 100 weight parts, the Dopamine HCL of 5 parts mixes in 200 parts of Tris damping fluids (pH8.5), reacts 24 hours, repeatedly dry at 70 DEG C after washing.
2) by the PE (melting index 11.5) of 10 weight parts, the modified Ag powder of 90 parts, the irradiation sensitizing agent triallylcyanurate of 0.05 part, the antioxidant 1010 of 0.02 part at room temperature mixes, and sending into length-to-diameter ratio is extruding pelletization in the twin screw extruder of 36 (being designated as pellet A).Wherein, forcing machine rotating speed is 20r/min, and the temperature range that forcing machine is each section is: feeding section 150-170 DEG C, melt zone 190-200 DEG C, mixing section 190-200 DEG C, exhaust section 170-190, homogenizing zone 160-180 DEG C.
Embodiment 2
The 3D that a kind of matrix material of embodiment 1 is obtained prints goods
The pellet A obtained in embodiment 1 is added the shower nozzle of 3D printer, by heat fused in shower nozzle, shower nozzle is along part section profile and fill orbiting motion, is extruded by the material of fusing simultaneously, utilizes the thermally melting of material, cohesiveness, extrude rear rapid solidification under the control of the computer, and use electron beam to carry out irradiation (electron accelerator energy is 0.5MeV, power 50KW, and irradiation dose is 5KGy), make crosslink material, layer by layer stack shaping.
The 3D obtained prints goods and has excellent hardness, dimensional stability and electroconductibility.
Embodiment 3
A kind of high filler loading capacity micro nano powder/polymer composites printed for 3D
1) by the 500nmAl of 100 weight parts 2o 3powder, the Silane coupling agent KH550 of 10 parts mixes in 200 parts of water, reacts 24 hours at 60 DEG C, repeatedly dry at 70 DEG C after washing.
2) by the PP (melting index 12.2) of 15 weight parts, the modified Al of 85 parts 2o 3powder, the irradiation sensitizing agent cyanacrylate of 0.1 part, the oxidation inhibitor 1096 of 0.01 part at room temperature mixes, and sending into length-to-diameter ratio is extruding pelletization in the twin screw extruder of 36 (being designated as pellet B).Wherein, forcing machine rotating speed is 40r/min, and the temperature range that forcing machine is each section is: feeding section 150-170 DEG C, melt zone 190-200 DEG C, mixing section 190-200 DEG C, exhaust section 170-190, homogenizing zone 160-180 DEG C.
Embodiment 4
The 3D that a kind of matrix material of embodiment 3 is obtained prints goods
The pellet B obtained in embodiment 3 is added the shower nozzle of 3D printer, by heat fused in shower nozzle, shower nozzle is along part section profile and fill orbiting motion, is extruded by the material of fusing simultaneously, utilizes the thermally melting of material, cohesiveness, extrude rear rapid solidification under the control of the computer, and use electron beam to carry out irradiation (electron accelerator energy is 0.75MeV, power 75KW, and irradiation dose is 10KGy), make crosslink material, layer by layer stack shaping.
The 3D obtained prints goods and has excellent physical strength, dimensional stability and thermal conductivity.
Embodiment 5
A kind of high filler loading capacity micro nano powder polymer composites printed for 3D
1) by 1 of 100 weight parts μm of CaCO 3powder, the silane coupling agent KH560 of 15 parts mixes in 200 parts of water, reacts 24 hours at 60 DEG C, repeatedly dry at 70 DEG C after washing.
2) by the PA (melting index 10.5) of 20 weight parts, the modified CaCO of 80 parts 3powder, the irradiation sensitizing agent trimethylolpropane trimethacrylate of 0.2 part, the oxidation inhibitor 1098 of 0.01 part at room temperature mixes, and sending into length-to-diameter ratio is extruding pelletization in the twin screw extruder of 36 (being designated as pellet C).Wherein, forcing machine rotating speed is 60r/min, and the temperature range that forcing machine is each section is: feeding section 150-170 DEG C, melt zone 190-200 DEG C, mixing section 190-200 DEG C, exhaust section 170-190, homogenizing zone 160-180 DEG C.
Embodiment 6
The 3D that a kind of matrix material of embodiment 5 is obtained prints goods
The pellet C obtained in embodiment 5 is added the shower nozzle of 3D printer, by heat fused in shower nozzle, shower nozzle is along part section profile and fill orbiting motion, is extruded by the material of fusing simultaneously, utilizes the thermally melting of material, cohesiveness, extrude rear rapid solidification under the control of the computer, and use electron beam to carry out irradiation (electron accelerator energy is 1MeV, power 100KW, and irradiation dose is 15KGy), make crosslink material, layer by layer stack shaping.
The 3D obtained prints goods and has excellent physical strength, dimensional stability and thermotolerance.
Embodiment 7
A kind of high filler loading capacity micro nano powder polymer composites printed for 3D
1) by 4 of 100 weight parts μm of ZrO 2powder, the silane coupling agent KH570 of 20 parts mixes in 200 parts of water, reacts 24 hours at 60 DEG C, repeatedly dry at 70 DEG C after washing.
2) by the PC (melting index 15) of 25 weight parts, the modified ZrO of 75 parts 2powder, the irradiation sensitizing agent trimethylolpropane trimethacrylate of 0.05 part, the irgasfos 168 of 0.01 part at room temperature mixes, and sending into length-to-diameter ratio is extruding pelletization in the twin screw extruder of 36 (being designated as pellet D).Wherein, forcing machine rotating speed is 80r/min, and the temperature range that forcing machine is each section is: feeding section 150-170 DEG C, melt zone 190-200 DEG C, mixing section 190-200 DEG C, exhaust section 170-190, homogenizing zone 160-180 DEG C.
Embodiment 8
The 3D that a kind of matrix material of embodiment 7 is obtained prints goods
The pellet D obtained in embodiment 7 is added the shower nozzle of 3D printer, by heat fused in shower nozzle, shower nozzle is along part section profile and fill orbiting motion, is extruded by the material of fusing simultaneously, utilizes the thermally melting of material, cohesiveness, extrude rear rapid solidification under the control of the computer, and use electron beam to carry out irradiation (electron accelerator energy is 1.5MeV, power 125KW, and irradiation dose is 20KGy), make crosslink material, layer by layer stack shaping.
The 3D obtained prints goods and has excellent physical strength, dimensional stability, thermotolerance and wear resistance.
Embodiment 9
A kind of high filler loading capacity micro nano powder polymer composites printed for 3D
1) by 10 of 100 weight parts μm of polynite powders, the silane coupling agent KH792 of 20 parts mixes in 200 parts of water, reacts 24 hours at 60 DEG C, repeatedly dry at 70 DEG C after washing.
2) by the EVA (melting index 20.3) of 30 weight parts, the modified polynite powder of 70 parts, the irradiation sensitizing agent trimethylolpropane trimethacrylate of 0.05 part, the irgasfos 168 of 0.02 part at room temperature mixes, and sending into length-to-diameter ratio is extruding pelletization in the twin screw extruder of 36 (being designated as pellet E).Wherein, forcing machine rotating speed is 100r/min, and the temperature range that forcing machine is each section is: feeding section 150-170 DEG C, melt zone 190-200 DEG C, mixing section 190-200 DEG C, exhaust section 170-190, homogenizing zone 160-180 DEG C.
Embodiment 10
The 3D that a kind of matrix material of embodiment 9 is obtained prints goods
The pellet E obtained in embodiment 9 is added the shower nozzle of 3D printer, by heat fused in shower nozzle, shower nozzle is along part section profile and fill orbiting motion, is extruded by the material of fusing simultaneously, utilizes the thermally melting of material, cohesiveness, extrude rear rapid solidification under the control of the computer, and use electron beam to carry out irradiation (electron accelerator energy is 2MeV, power 150KW, and irradiation dose is 5KGy), make crosslink material, layer by layer stack shaping.
The 3D obtained prints goods and has excellent physical strength, dimensional stability and flame retardant resistance.
Embodiment 11
A kind of high filler loading capacity micro nano powder polymer composites printed for 3D
1) by 10 of 100 weight parts μm of lithium algae soil powders, the silane coupling agent DL602 of 15 parts mixes in 200 parts of water, reacts 24 hours at 60 DEG C, repeatedly dry at 70 DEG C after washing.
2) by the ABS (melting index 14.5) of 10 weight parts, the modified lithium algae soil powder of 90 parts, the irradiation sensitizing agent trimethylolpropane trimethacrylate of 0.05 part, the irgasfos 168 of 0.02 part at room temperature mixes, and sending into length-to-diameter ratio is extruding pelletization in the twin screw extruder of 36 (being designated as pellet F).Wherein, forcing machine rotating speed is 100r/min, and the temperature range that forcing machine is each section is: feeding section 150-170 DEG C, melt zone 190-200 DEG C, mixing section 190-200 DEG C, exhaust section 170-190, homogenizing zone 160-180 DEG C.
Embodiment 12
The 3D that a kind of matrix material of embodiment 11 is obtained prints goods
The pellet F obtained in embodiment 11 is added the shower nozzle of 3D printer, by heat fused in shower nozzle, shower nozzle is along part section profile and fill orbiting motion, is extruded by the material of fusing simultaneously, utilizes the thermally melting of material, cohesiveness, extrude rear rapid solidification under the control of the computer, and use electron beam to carry out irradiation (electron accelerator energy is 2MeV, power 150KW, and irradiation dose is 5KGy), make crosslink material, layer by layer stack shaping.
The 3D obtained prints goods and has excellent physical strength, dimensional stability and flame retardant resistance.
Embodiment 13
A kind of high filler loading capacity micro nano powder polymer composites printed for 3D
By the ABS (melting index 14.5) of 10 weight parts, the lithium algae soil powder of 90 parts, the irradiation sensitizing agent trimethylolpropane trimethacrylate of 0.05 part, the irgasfos 168 of 0.02 part at room temperature mixes, and sending into length-to-diameter ratio is extruding pelletization in the twin screw extruder of 36 (being designated as pellet F1).Wherein, forcing machine rotating speed is 100r/min, and the temperature range that forcing machine is each section is: feeding section 150-170 DEG C, melt zone 190-200 DEG C, mixing section 190-200 DEG C, exhaust section 170-190, homogenizing zone 160-180 DEG C.
Embodiment 14
The 3D that a kind of matrix material of embodiment 13 is obtained prints goods
The pellet F obtained in embodiment 11 is added the shower nozzle of 3D printer, by heat fused in shower nozzle, shower nozzle is along part section profile and fill orbiting motion, is extruded by the material of fusing simultaneously, utilizes the thermally melting of material, cohesiveness, extrude rear rapid solidification under the control of the computer, and use electron beam to carry out irradiation (electron accelerator energy is 2MeV, power 150KW, and irradiation dose is 5KGy), make crosslink material, layer by layer stack shaping.
The 3D that obtained prints goods and has excellent physical strength (goods lower slightly compared with embodiment 12), dimensional stability and flame retardant resistance.

Claims (21)

1. goods, it prints obtained by a kind of high filler loading capacity micro nano powder/polymer composites for 3D printing by 3D;
Described high filler loading capacity micro nano powder/polymer composites for 3D printing is using micro nano powder as body material, and fluoropolymer resin is as binding agent, and raw material and the content thereof of described material comprise:
Micro nano powder 90-70 weight part,
Fluoropolymer resin 10-30 weight part,
Irradiation sensitizing agent 0.05-0.2 weight part.
2. goods according to claim 1, is characterized in that, described matrix material is obtained by the method for the mixing and screw extrusion press extruding pelletization that comprise raw material.
3. goods according to claim 1 and 2, is characterized in that, described micro nano powder refers to the particulate matter of particle diameter between 1 nanometer and 100 microns; Described micro nano powder is inorganic micro nano powder.
4. goods according to claim 3, it is characterized in that, described inorganic micro nano powder be selected from metal simple-substance powder, metal-oxide powder, non-metal simple-substance powder, silver halide powder, carbonate powder, phosphate powder, silicate powder and clay class powder one or more; The particle diameter of described micro nano powder is between 50nm and 10 μm.
5. goods according to claim 3, is characterized in that, described micro nano powder is through the micro nano powder of surface modifying agent.
6. goods according to claim 5, is characterized in that, described surface-modifying agent be selected from Dopamine HCL and silane coupling agent one or more, described silane coupling agent is selected from KH550, KH560, KH570, KH792 or DL602.
7. goods according to claim 1 and 2, is characterized in that, described fluoropolymer resin is thermoplastic resin; Described thermoplastic resin be selected from polyolefine, polymeric amide, polycarbonate, polyoxymethylene, ethylene-vinyl acetate copolymer, polyester, acrylonitrile-butadiene-styrene copolymer, styrene-butadiene-styrene block copolymer, styrene isoprene styrene block copolymer (SIS), transparent butadiene-styrene impact resin, polyacrylic ester one or more.
8. goods according to claim 7, is characterized in that, described polyolefine is selected from PE, PP or PVC, and described polyester is selected from PET, PBT, PCL or PLA.
9. goods according to claim 1 and 2, is characterized in that, the melting index of selected fluoropolymer resin is at least greater than 10.
10. goods according to claim 1 and 2, it is characterized in that, described radiosensitizer be selected from triallylcyanurate, cyanacrylate, three methylpropenyl isocyanic ester, trimethylolpropane trimethacrylate, Viscoat 295, trimesic acid triallyl, diallyl isocyanic ester, m-phthalic acid two propylene, bismaleimides, dimethacrylate triethyleneglycol ester, dimethacrylate glycol ether ester one or more.
11. goods according to claim 1 and 2, is characterized in that, also comprise in described raw material:
Oxidation inhibitor 0.01-0.02 part.
12. goods according to claim 11, is characterized in that, described oxidation inhibitor is Hinered phenols antioxidant and/or phosphorous acid esters auxiliary antioxidant.
13. goods according to claim 12, is characterized in that, described oxidation inhibitor is selected from antioxidant 1010: four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Oxidation inhibitor 1096:IRGANOXB-1096; Primary antioxidant 1098:(N, N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine) and phosphite ester kind antioxidant interworking thing; And irgasfos 168: one or more in three [2,4-di-tert-butyl-phenyl] phosphorous acid ester.
14. goods according to claim 1 and 2, is characterized in that, the raw material of described material and content thereof are:
The preparation method of the goods described in 15. any one of claim 1 to 14, is characterized in that, the high filler loading capacity micro nano powder/polymer composites for 3D printing wherein adopts the method preparation comprised the following steps:
The mixing of raw material and the step of screw extrusion press extruding pelletization.
16. preparation methods according to claim 15, is characterized in that, the preparation method of described material specifically comprises:
1) modification of micro nano powder;
2) mixing of each raw material;
3) screw extrusion press extruding pelletization.
17. preparation methods according to claim 16, is characterized in that, above-mentioned steps 1) be specially: the surface-modifying agent of described micro nano powder 5-20 part of 100 weight parts is carried out surface modification in the solution;
Described step 2) and 3) be specially: by the fluoropolymer resin of 10-30 weight part, the modified micro nano powder of 90-70 part, the irradiation sensitizing agent of 0.05-0.2 part, the oxidation inhibitor of 0.01-0.02 part at room temperature mixes, sending into length-to-diameter ratio is extruding pelletization in the twin screw extruder of 36, forcing machine rotating speed is 20-100r/min, and the temperature range that forcing machine is each section is: feeding section 150-170 DEG C, melt zone 190-200 DEG C, mixing section 190-200 DEG C, exhaust section 170-190 DEG C, homogenizing zone 160-180 DEG C.
The preparation method of the goods described in 18. any one of claim 1-14, comprises the step printed by 3D by the described high filler loading capacity micro nano powder/polymer composites being used for 3D printing.
19. preparation methods according to claim 18, is characterized in that, described step specifically comprises:
The pellet of described matrix material is added the shower nozzle of 3D printer, by heat fused in shower nozzle, shower nozzle is along part section profile and fill orbiting motion, the material of fusing is extruded simultaneously, extrude rear rapid solidification under the control of the computer, and use electron beam to carry out irradiation, make crosslink material, layer by layer stack shaping.
20. preparation methods according to claim 19, is characterized in that, the parameter of described irradiation specifically: electron accelerator energy is 0.3-5MeV, power 50-150KW, and irradiation dose is 5-20KGy.
The purposes of the high filler loading capacity micro nano powder/polymer composites for 3D printing in the goods described in 21. any one of claim 1 to 14, it prints for 3D.
CN201410183157.2A 2014-04-30 2014-04-30 A kind of high filler loading capacity micro nano powder/polymer composites for 3D printing and preparation method thereof and goods Active CN103980592B (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201410183157.2A CN103980592B (en) 2014-04-30 2014-04-30 A kind of high filler loading capacity micro nano powder/polymer composites for 3D printing and preparation method thereof and goods
US15/507,670 US11299569B2 (en) 2014-04-30 2015-04-24 Material for 3D printing, process for preparing the same and article thereof
PCT/CN2015/077360 WO2015165363A1 (en) 2014-04-30 2015-04-24 Material for 3d printing and preparation method therefor and product thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410183157.2A CN103980592B (en) 2014-04-30 2014-04-30 A kind of high filler loading capacity micro nano powder/polymer composites for 3D printing and preparation method thereof and goods

Publications (2)

Publication Number Publication Date
CN103980592A CN103980592A (en) 2014-08-13
CN103980592B true CN103980592B (en) 2016-02-24

Family

ID=51272775

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410183157.2A Active CN103980592B (en) 2014-04-30 2014-04-30 A kind of high filler loading capacity micro nano powder/polymer composites for 3D printing and preparation method thereof and goods

Country Status (1)

Country Link
CN (1) CN103980592B (en)

Families Citing this family (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015165363A1 (en) * 2014-04-30 2015-11-05 中国科学院化学研究所 Material for 3d printing and preparation method therefor and product thereof
CN104193919A (en) * 2014-08-26 2014-12-10 太仓碧奇新材料研发有限公司 Polyethylene terephthalate composite material for 3D printing and preparation method thereof
CN104310948B (en) * 2014-09-10 2016-01-20 济南大学 A kind of three D print the preparation method of rapid shaping inorganic powder materials
CN104497462A (en) * 2014-12-11 2015-04-08 江苏金发科技新材料有限公司 Thermoplastic for additive manufacturing applied to fused deposition technology
CN104479349B (en) * 2014-12-18 2017-12-01 陈梓煜 A kind of flame-proof composite material for 3D printing and preparation method thereof
CN104497562A (en) * 2014-12-18 2015-04-08 陈梓煜 Nylon-based material for 3D (three-dimensional) printing and preparation method thereof
CN107111225B (en) 2014-12-23 2021-07-27 普利司通美国轮胎运营有限责任公司 Additive manufacturing method of polymer product
CN107209648B (en) * 2015-01-30 2020-06-23 惠普发展公司有限责任合伙企业 Adjustment of halftone threshold
CN104672755A (en) * 2015-02-05 2015-06-03 中国科学院福建物质结构研究所 Nano composite material for melt deposition type 3D printers and preparation method thereof
CN104961885B (en) * 2015-06-29 2017-08-25 殷明 A kind of exfoliated polyester/clay nano composite material and preparation method thereof
CN105860517B (en) * 2015-10-29 2018-09-04 福建易达纳米材料科技有限公司 A kind of environmental protection 3D printing consumptive material and its production technology
CN105440664A (en) * 2015-10-30 2016-03-30 福建易达纳米材料科技有限公司 3D printing consumable with abrasive material and manufacturing method for 3D printing consumable
CN105218939B (en) * 2015-11-05 2017-10-27 中国科学院福建物质结构研究所 A kind of foamable 3D printing material and preparation method thereof
US11097531B2 (en) 2015-12-17 2021-08-24 Bridgestone Americas Tire Operations, Llc Additive manufacturing cartridges and processes for producing cured polymeric products by additive manufacturing
CN106893279A (en) * 2015-12-18 2017-06-27 四川鑫达企业集团有限公司 A kind of biodegradable 3D printing toughening material and preparation method
CN105669160A (en) * 2015-12-31 2016-06-15 桂林森林美实木家具有限公司 Preparation method of illite smectite clay 3D printing powder
CN105504726A (en) * 2016-02-03 2016-04-20 黑龙江鑫达企业集团有限公司 Composite material suitable for 3D printing and preparation method thereof
CN105885330A (en) * 2016-04-25 2016-08-24 中国科学院宁波材料技术与工程研究所 Organically modified attapulgite/ABS composite, preparation method thereof and application of organic modified attapulgite/ABS composite in 3D printing
CN105733271A (en) * 2016-05-09 2016-07-06 李红玉 Polymer material used for 3D printing and preparation method thereof
CN105778395A (en) * 2016-05-20 2016-07-20 江苏浩宇电子科技有限公司 3D printing material with function of trapping and killing insects and preparation method thereof
US9815612B1 (en) 2016-06-09 2017-11-14 Avanti USA Ltd. Flip-top bushing for aerosol canister with molded actuator spring
CN106186810B (en) * 2016-07-22 2018-06-29 河北虹天电气科技有限公司 A kind of 3D printing construction material
CN106146959A (en) * 2016-08-01 2016-11-23 苏州秉创科技有限公司 A kind of plant base degradable 3D printed material
CN106433108B (en) * 2016-09-19 2019-03-26 广东银禧科技股份有限公司 A method of its progress 3D printing of high temperature resistant nylon silk material for 3D printing and its preparation method and application
EP3532267B1 (en) 2016-10-27 2023-03-01 Bridgestone Americas Tire Operations, LLC Processes for producing cured polymeric products by additive manufacturing
CN106633596A (en) * 2016-11-25 2017-05-10 安徽省春谷3D打印智能装备产业技术研究院有限公司 3D (three-dimensional) printing wire and method for preparing same
CN107312287A (en) * 2017-06-19 2017-11-03 合肥斯科尔智能科技有限公司 A kind of aerospace industry high temperature resistant 3D printing material and preparation method thereof
CN107163492A (en) * 2017-06-19 2017-09-15 合肥斯科尔智能科技有限公司 A kind of auto manufacturing high-temperature resistant anti-corrosive 3D printing material and preparation method thereof
CN107177155A (en) * 2017-06-19 2017-09-19 合肥斯科尔智能科技有限公司 A kind of building field 3D printing material of high intensity UV resistant and preparation method thereof
DE102017118831A1 (en) * 2017-08-17 2019-02-21 Eos Gmbh Electro Optical Systems Method and device for the additive production of at least one component layer of a component and storage medium
CN107603201B (en) * 2017-09-07 2021-02-26 金华造物新材料有限公司 3D printing photosensitive resin for precision casting of ornaments and dentistry
CN107746501B (en) * 2017-11-09 2021-02-12 王臻 Material for 3D printing and preparation method thereof
CN108587040A (en) * 2017-12-31 2018-09-28 芜湖林电子科技有限公司 A kind of 3D printing ABS composite material and preparation method thereof that good toughness is ageing-resistant
CN109575441B (en) * 2018-12-12 2021-07-30 上海金发科技发展有限公司 Polyolefin composite material with good appearance for 3D printing and preparation method thereof
USD892628S1 (en) 2019-01-11 2020-08-11 Albert P. Caruso Aerosol canister case with indication ring
CN111060234B (en) * 2019-12-30 2023-11-28 浙江清华柔性电子技术研究院 Functional slurry and application thereof
CN114276604B (en) * 2021-12-31 2023-08-18 江苏达胜高聚物股份有限公司 High-insulation photovoltaic cable material and preparation method and application thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1358791A (en) * 2000-12-12 2002-07-17 海尔科化工程塑料国家工程研究中心有限公司 Polymer organic nano composite ocmposition for making agriculture greenhouse film and preparation process thereof
CN1631907A (en) * 2004-11-25 2005-06-29 复旦大学 Method for preparing polymer/inorganic nano composite material powder initiated by nano semiconductor
CN1673267A (en) * 2005-03-23 2005-09-28 中山大学 Microfiber technology process of preparing nanometer composite inorganic particle/polymer material
WO2006090804A1 (en) * 2005-02-23 2006-08-31 Mitsubishi Chemical Corporation Semiconductor light emitting device member, method for manufacturing such semiconductor light emitting device member and semiconductor light emitting device using such semiconductor light emitting device member
CN101092506A (en) * 2007-06-26 2007-12-26 上海大学 Nano composite material of copolyester, and preparation method
CN102520598A (en) * 2011-12-12 2012-06-27 珠海天威飞马打印耗材有限公司 Charging roller and manufacturing method thereof
CN103012901A (en) * 2012-12-13 2013-04-03 广东天安新材料股份有限公司 Easy-to-mold automotive interior material
WO2013094759A1 (en) * 2011-12-21 2013-06-27 三菱レイヨン株式会社 Polymer powder, curable resin composition, and cured product thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1358791A (en) * 2000-12-12 2002-07-17 海尔科化工程塑料国家工程研究中心有限公司 Polymer organic nano composite ocmposition for making agriculture greenhouse film and preparation process thereof
CN1631907A (en) * 2004-11-25 2005-06-29 复旦大学 Method for preparing polymer/inorganic nano composite material powder initiated by nano semiconductor
WO2006090804A1 (en) * 2005-02-23 2006-08-31 Mitsubishi Chemical Corporation Semiconductor light emitting device member, method for manufacturing such semiconductor light emitting device member and semiconductor light emitting device using such semiconductor light emitting device member
CN1673267A (en) * 2005-03-23 2005-09-28 中山大学 Microfiber technology process of preparing nanometer composite inorganic particle/polymer material
CN101092506A (en) * 2007-06-26 2007-12-26 上海大学 Nano composite material of copolyester, and preparation method
CN102520598A (en) * 2011-12-12 2012-06-27 珠海天威飞马打印耗材有限公司 Charging roller and manufacturing method thereof
WO2013094759A1 (en) * 2011-12-21 2013-06-27 三菱レイヨン株式会社 Polymer powder, curable resin composition, and cured product thereof
CN103012901A (en) * 2012-12-13 2013-04-03 广东天安新材料股份有限公司 Easy-to-mold automotive interior material

Also Published As

Publication number Publication date
CN103980592A (en) 2014-08-13

Similar Documents

Publication Publication Date Title
CN103980592B (en) A kind of high filler loading capacity micro nano powder/polymer composites for 3D printing and preparation method thereof and goods
CN103980591B (en) A kind of electron radiation crosslinked polymeric materials for 3D printing and preparation method thereof and goods
US11299569B2 (en) Material for 3D printing, process for preparing the same and article thereof
CN104031304B (en) A kind of ultraviolet light cross-linking polymer materials for 3D printing and its preparation method and application
CN103980594B (en) A kind of uv-radiation crosslinked polymeric materials for 3D printing and preparation method thereof and goods
Cheng et al. 3D printing of electrochemical energy storage devices: a review of printing techniques and electrode/electrolyte architectures
Bai et al. Improving the mechanical properties of laser‐sintered polyamide 12 through incorporation of carbon nanotubes
KR101610218B1 (en) Complex filament composition for fdm type 3d printer containing metal powder
CN103980410B (en) A kind of composition and method of making the same for 3D printing and goods
CN104308072B (en) Carbon fiber-based precoated sand material for selective laser sintering and preparation method thereof
CN105542377A (en) Preparation method of conductive 3D printing supplies by using double screw extruder
CN103980593A (en) Modified high density polyethylene 3D printing moulding material and preparation method
CN103992473B (en) The heat conduction height that a kind of 3D of can be used for prints glues nylon powder body and preparation method thereof
CN105778484B (en) The modified nylon materials and its Method of printing of a kind of 3D printing applied to FDM technology
CN105713362A (en) Composition used for 3D printing, 3D printing material containing composition, preparation method and applications of 3D printing material as well as 3D printing equipment
CN105504471A (en) Environment-friendly and antibacterial material for 3D printing and preparation method of material
CN107151443A (en) A kind of PEI base graphene 3D printing composite and preparation method thereof
CN105623029B (en) Composite reinforcing agent, PC/PBT alloy and application
CN103333394B (en) A kind of preparation method designing polymer-based carbon functional membrane
CN105504749A (en) Polycarbonate composite material for 3D printing and preparation method thereof
CN104672755A (en) Nano composite material for melt deposition type 3D printers and preparation method thereof
CN108219349A (en) A kind of 3D printing modified ABS resin and preparation method thereof
KR101905710B1 (en) Basalt fiber-filled thermoplastic filament for 3D printing and fiber reinforced composite prepared by using the same
CN107189423A (en) Method based on FDM3D antifriction materials printed and preparation method thereof and enhancing material product Wear vesistance
CN101942137B (en) Method for preparing conductivity-enhanced polymer/carbon nano tube composite material by vibration injection molding device

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant