CN100503703C - Negative poisson's ratio material and its preparing method and use - Google Patents
Negative poisson's ratio material and its preparing method and use Download PDFInfo
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- CN100503703C CN100503703C CNB2005101306833A CN200510130683A CN100503703C CN 100503703 C CN100503703 C CN 100503703C CN B2005101306833 A CNB2005101306833 A CN B2005101306833A CN 200510130683 A CN200510130683 A CN 200510130683A CN 100503703 C CN100503703 C CN 100503703C
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- 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
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
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- 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
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
- B29C44/08—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles using several expanding or moulding steps
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- 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
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/35—Component parts; Details or accessories
- B29C44/355—Characteristics of the foam, e.g. having particular surface properties or structure
- B29C44/357—Auxetic foams, i.e. material with negative Poisson ratio; anti rubber; dilatational; re-entrant
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
Abstract
The present invention relates to composite polymer material, and is especially stretching material with negative Poisson's ratio and its preparation process and use. The foamed material obtained through secondary foaming process or screw extrusion foaming process has microscopic double fan-shaped composite structure with middle layer of regular honeycomb structure, outer layer of ordered gradually lengthened arrangement and micropores of 80-150 micron size. The foamed material has the mechanical performance of perpendicularly expanding while being stretched and perpendicularly contracting while being extruded. By means of special preparation process, the foamed material may have raised compression resistance, shock absorption, rebound elasticity and other mechanical performance. The unique mechanical performance makes the material possess application in composite board, waste water treatment, deep water job and other fields.
Description
Technical field
Negative poisson's ratio material of the present invention belongs to the high performance polymer matrix material, particularly the structural models of the mechanical property of material and material.The negative poisson's ratio material that can be widely used in fields such as composite sheet, wastewater treatment, deepwater work, space flight and aviation, comfort fabrics, embedded workpiece, and this preparation methods and purposes.
Background technology
We in the middle of the common material, the scope of its Poisson's ratio (Poisson ' s ratio), major part all is within positive 0 to 0.5, yet the Poisson's ratio of most material is between 0.2 to 0.4.However, still the material that has a minority has the character of negative poisson ' s ratio (negativePoisson ' s ratio), for example: the Poisson's ratio of monocrystalline sulphide ores (single crystal pyrite) for-0.14, the Poisson's ratio of α-cristobalite also can reach-0.5.Simultaneously, viewpoint from theory, the special property of negative poisson ' s ratio as far back as nineteen sixty-eight by B.M.Lempriere, utilize elastic strain energy theory (strain energy in the theory of elasticity) to prove, be-1＜v＜0.5 with the Poisson's ratio scope of tropism's material.But not the Poisson's ratio scope of isotropic materials then must meet: v ij≤(Ei/Ej)
1/2And the condition of v ij Ej=v ji Ei.
The character of this material can be defined as follows:
V=-transvrsal strain/longitudinal strain
V is when general material load one drawing force, and side direction has shrinkage phenomenon; Otherwise in the time of by compression, then side direction has the generation of expansible phenomenon.Therefore, the Poisson ratio of general material all be present on the occasion of, what will introduce in the present invention so then is a kind of traditional concept that is different from, the structured material with negative poisson ' s ratio character.
The negative poisson ' s ratio characteristic of material is not the mechanical properties from material itself, but because the special microstructure of material internal, therefore, negative poisson's ratio material also is a kind of microporous materials.Generally speaking, more common negative poisson ' s ratio structure has following two kinds:
1. inner concave shape foam structure
Inner concave shape foam structure is by traditional sponge material, makes via heating, pressurizeing to form.These materials can bear interior curve distortion, and produce lateral expansion in axial pulling load, and this causes volume and negative poisson ' s ratio comprehensively to increase.Some can be close to-1 to these kinds etc. to the negative poisson ' s ratio of material.The mechanical properties that changes traditional foam material in theory has two kinds of methods: a kind of is to change its chemical composition, and another kind is exactly the geometrical shape that changes hole shape.Research major part in this field all was towards the chemical constitution that changes foam in the past, yet research in recent years is to trend towards changing the geometrical shape in foam hole.
2. fiber-particle reticulated structure
This kind telescopic material is the multi-cellular structure material different with traditional sponge material.Its microstructure is to be arranged with fibrous web-like by the anisotropic particle to link mutually.When it is subjected to axially drawing load, at first be to draw under the load, because the interparticle fiber of contact anisotropic becomes tight, and cause the transverse deflection of anisotropic particle.Second is exactly the transverse deflection of anisotropic particle rotation itself.
Except above two kinds of structures, the multilayer materials thin plate also is common a kind of material with negative poisson ' s ratio effect.As long as the multilayer materials of suitable angle is made symmetry to be arranged, because the restraining function between each layer, just can cause the negative poisson ' s ratio effect at thickness direction, for example: the Poisson ratio of glass fibre-Resins, epoxy (graphite-epoxy) MULTILAYER COMPOSITE thin plate can reach-0.21.Similarly, also non-itself the material character of the negative poisson ' s ratio effect of this class material, but because the multiple layering effect between the composite thin plate.
Negative Poisson material also has following character:
(1) shock absorption power (impact absorption)
(2) damage resistibility (damage resistance)
(3) damage permissible tolerance (damage tolerance)
(4) plane strain strength at break (plane strain fracture toughness)
(5) rebound resilience (resilience)
(6) shearing modulus (shearing modulus)
(7) depression resistibility (indentation resistance)
Therefore, this class material is compared with other material, has very big advantage.
Summary of the invention
An object of the present invention is to provide a kind of negative poisson's ratio material, it is based on a kind of microporous materials of configuration aspects.This microporous materials has the mechanical property more higher than common material, shows the raising of compressive strength and Young's modulus.
Another object of the present invention provides a kind of preparation method of negative poisson's ratio material.
The purposes that also has a purpose to provide a kind of negative poisson's ratio material of the present invention.
We find when research natural polymer foam material, when the hexagon micropore of comparison rule changes with the stressing conditions that elongates micropore, the compressive strength and the Young's modulus of elongating micropore increase many, thus, we can design similar porous structure material, promptly have the porous material of negative poisson ' s ratio.
Negative poisson's ratio material of the present invention is the sandwich that is prepared by natural polymer and/or synthesized polymer material, whipping agent 1, whipping agent 2 and softening agent, the foams of this material have and are biflabellate composite structure, the middle layer of composite structure is the polygonal polynuclear plane of rule, the skin of composite structure is outside by the center, in the radial direction, gradually become the extended polynuclear plane, the skin of composite structure is the gradually long ordered arrangement of divergent shape, and the aperture of its micropore is 80～150 μ m.
Described whipping agent 1 is butane, pentane or their mixture.
Described whipping agent 2 is higher amino derivatives of boiling point (108 ℃ of amine decomposition temperatures), (heat decomposition temperature is greater than 120 ℃ for the azo class.) or their mixture, amino derivative is N, N ＇-dimethyl-N, N ＇-dinitrosoterephthalamine; The azo class is a Cellmic C 121.
The polygonal middle layer of the radial direction of described sandwich is pentagon or hexagon; The two outer field polynuclear planes up and down of sandwich are extended hexagons or microscler.
Described sandwich is by a skin, a middle layer, a skin, a middle layer, a skin, by that analogy, obtains the multi-layer compound structure material.
Its vertical direction had swelling property when described negative poisson's ratio material had tension, and/or had when being squeezed and shrink and the mechanical property of extruding and compression property.
Each component concentration of described negative poisson's ratio material is:
Natural polymer and/or synthesized polymer material 85.0wt%～90.0wt%
Whipping agent 1 0.5wt%～2.0wt%
The softening agent surplus.
Described natural macromolecular material is starch, Mierocrystalline cellulose or their mixture etc.Synthetic macromolecule is poly butylene succinate (PBS), poly-several lactones (PCL), poly(lactic acid) (PLA), polyethylene (PE), polypropylene (PP), polystyrene (PS) or their any mixture etc.
Described softening agent is glycerol, sorbyl alcohol, propylene glycol, glycerine three acid anhydride esters, glycerine list acid anhydride ester or their mixture.
Negative poisson's ratio material of the present invention is prepared by second time of foaming method or screw rod extrusion foaming method, and the prescription of material and content are:
Natural polymer and/or synthesized polymer material 85.0wt%～90.0wt%;
Whipping agent 1 0.5wt%～2.0wt%;
The softening agent surplus.
Whipping agent 1 is different with whipping agent 2, and one is low-boiling point material, and another boiling point is a little more than previous, can adopt second time of foaming like this.
A. the second time of foaming method may further comprise the steps:
(1) preparation of homogeneous phase microcellular foam material
Raw material in the above-mentioned prescription is proportionally mixed, and high-speed stirring mixes, and directly puts into mould, perhaps makes sheet material and be placed in the mould again in two rollers, foams under 70～150 ℃ of temperature, is prepared into well-regulated foam sheet or sheet material; As middle layer or internal layer;
(2) preparation of directed microcellular foam material
Raw material in the above-mentioned prescription proportionally mixed being placed in the fan-shaped mould, foamable on fan-shaped mould remains on more than 125 ℃ temperature, makes its directed foaming, makes the sheet material or the sheet material of directed foaming; As skin;
(3) preparation of negative poisson's ratio material
Sheet material that step (1) is obtained or sheet material are combined with each other in the middle of being placed on sheet material that step (2) obtains or sheet material, be the sheet material or the sheet material of two-layer step (2), the centre sandwiches the sheet material or the sheet material of one deck step (1), form microtexture and be biflabellate three-decker, direct heat lumps together then, perhaps use sizing agent to bond together, be prepared into the foam sheet or the sheet material of negative poisson's ratio material; Or the sheet material or the sheet material that directly step (1) are obtained are put into the segmental mould, put into the material of prescription again on the both sides up and down of this sheet material or sheet material, directly, be prepared into the foam sheet or the sheet material of negative poisson's ratio material at the directed foaming in the both sides up and down in middle layer; Or
B. screw rod extrusion foaming method may further comprise the steps:
Select the screw rod of two kinds of identical bores or different bores, according to the cell size of foam material, the requirement difference of density size, the temperature of the extruder head of the screw rod of control forcing machine and the temperature of fan-shaped mould, wherein the temperature of the extruder head of screw rod is 70～125 ℃, and the temperature of fan-shaped mould is 130～135 ℃; The screw rod bore of extruding the ectonexine foams is identical, or outer screw rod bore greater than the middle layer;
Will be by the middle layer foam that screw rod is extruded through the two rollers of 80～125 ℃ heat, the outer material of extruding by screw rod is the two rollers of heat outside and then, at outer material through the material both sides, middle layer behind the overheated pair of roller are compound, again through the two rollers of the heat of 125～130 ℃ of excess temperatures, directed foaming in mould then is prepared into the foam sheet or the board product of negative poisson's ratio material.
Four sections temperature of described middle layer screw rod are respectively 70～120 ℃; Four sections temperature of outer screw rod are respectively 110～120 ℃.
According to the preparation method of homogeneous phase microcellular foam material, preparation middle layer and skin; At the compound skin of the both sides in middle layer difference, be prepared into and comprise a middle layer and two outer field composite beds, then with their heat seals or be bonded together, a compound middle layer and a skin on a skin again, then with their heat seals or be bonded together, by that analogy, obtain the foam sheet or the board product of the negative poisson's ratio material of multi-layer microporous structure.
Negative poisson's ratio material of the present invention can be used as composite sheet, wastewater treatment, deepwater work, space flight and aviation, comfort fabrics or embedded workpiece material and uses.
The yield strength of foams of the present invention meets the anisotropic model that people such as (U.S.) Huber and Bibson propose.
E
sBe the solid Young's modulus, C is a rate constant, and t is a wall thickness, and l is the length of side, and h is a height.
Foams have and are biflabellate composite structure, the middle layer of composite structure is the polygonal polynuclear plane of rule, the skin of composite structure is outside by the center, in the radial direction, gradually become the extended polynuclear plane, the skin of composite structure is the gradually long ordered arrangement of divergent shape, the stressed changing conditions of negative poisson's ratio material as shown in Figure 2.When the material in Fig. 2 stretched when the reactive force that is subjected to P, vertical direction can broaden because of stressed, and width becomes b ＇ by b.Its negative poisson ' s ratio is to be obtained by following formula:
X: expression is subjected to the coordinate of force direction;
Y: expression vertically is subjected to the coordinate of force direction;
ε ＇: expression is subjected to the dimensional change ratio of force direction;
ε: expression vertically is subjected to the dimensional change ratio of force direction;
λ ＇, b ＇: represent respectively stressed before the length of x, y direction and wide;
λ, b: represent the length of stressed back x, y direction and wide respectively.
Ratio when axial compression is bigger, and the negative poisson ' s ratio phenomenon is obvious; Ratio during radial compression is less, and the negative poisson ' s ratio phenomenon is not obvious.
In " sandwich ", when compression, the centre is extruded contraction, negative poisson ' s ratio occurs in the radial direction similar.
What be worth that we pay close attention to is: the foams skin is the gradually long ordered arrangement of divergent shape, makes the raising of micropore axial stress greater than 80%, and Young's modulus improves more than 1 times, and density is constant substantially.And in actual applications, in most cases, require foam material only to need that mechanical properties such as higher compressive strength and Young's modulus are arranged on a certain direction.
According to above-mentioned principle, we can become material preparation " sandwich " structure of similar Fig. 1, and the middle layer is the Polygons of rule, as hexagon, two-layer up and down is extended hexagon or microscler, and the compressive strength and the Young's modulus of elongating on the direction at segmental increase significantly.Like this, keeping under the identical situation of density, mechanical property improves a lot.So such material can be widely used in aspects such as industry, military affairs, space flight.As can be used as composite sheet, wastewater treatment, deepwater work, space flight and aviation, comfort fabrics, embedded workpiece material and use.
When negative poisson's ratio material of the present invention has tension its vertical direction have expansion (stretching property) and (or) mechanical property of shrinking (extruding and compression property) when being squeezed, and, can improve the mechanical property such as crushing resistance, shock absorption power, rebound resilience of material by special manufacture craft.This special mechanical properties has determined its application prospect in fields such as composite sheet, wastewater treatment, deepwater work, space flight and aviation, comfort fabrics.
Description of drawings
Fig. 1. the structural representation with material of stretching property of the present invention.
Fig. 2. the stressed changing conditions synoptic diagram of negative poisson's ratio material of the present invention.
Embodiment
Embodiment 1
With starch 70g, PBS 15g, glycerol 8g, sorbyl alcohol 5g, Cellmic C 121 1.5g, N, N ＇-dimethyl-N, N ＇-dinitrosoterephthalamine 0.5g, proportionally preparation, extruding pelletization in screw extrusion press.Add a certain amount of above-mentioned particle according to required preparation foam size, 110～125 ℃ on even heating mould kept temperature 8～15 minutes.Be cooled to room temperature then and take out the goods object, as the middle layer, standby.
Above-mentioned sheet material of making or sheet material are placed in the another one fan-shaped mould, in this mould, foam sheet or sheet material are fixed in the middle of the mould, the mixture that the both sides of the sheet material in middle layer or sheet material is added above-mentioned prescription, the heating mould temperature is 130～135 ℃ rapidly, makes by expanded beads to be fan-shaped foaming rapidly in cavity.Be incubated 8～15 minutes, be cooled to room temperature then, take out goods, obtain negative poisson's ratio material, the aperture of its micropore is 80～150 μ m, and structure as shown in Figure 1.
With starch 85g, glycerol 10g, glycerine three acid anhydride ester 3g, Cellmic C 121 2.0g, according to certain ratio, extruding pelletization in screw extrusion press.Add a certain amount of above-mentioned particle according to required preparation foam size, 120～125 ℃ on even heating mould kept temperature 8～15 minutes.Be cooled to room temperature then and take out the goods object, as the middle layer, standby.
Above-mentioned sheet material of making or sheet material are placed in the another one fan-shaped mould, in this mould, foam sheet or sheet material are fixed in the middle of the mould, the mixture that the both sides of the sheet material in middle layer or sheet material is added above-mentioned prescription, the heating mould temperature is 130～135 ℃ rapidly, makes by expanded beads to be fan-shaped foaming rapidly in cavity.Be incubated 8～15 minutes, be cooled to room temperature then, take out goods, obtain negative poisson's ratio material, the aperture of its micropore is 80～150 μ m, and structure as shown in Figure 1.
Embodiment 3
With starch 82g, PBS15g, glycerol 10g, glycerine list acid anhydride ester 5g, N, N ＇-dimethyl-N, N ＇-dinitrosoterephthalamine 1.5g, Cellmic C 121 1.5g, according to certain ratio extrude in screw extrusion press, without granulation, directly extrusion moulding.
Four district's temperature of middle layer and outer screw rod are respectively 90～120 ℃, and 100 ℃ of extrusion temperature, the initial temperature of pressure roller and mould also are 110 ℃, controlled temperature.
With outer screw rod extrusion foaming body bifurcated, add outer foam in the both sides of middle layer screw rod extrusion foaming body, through two roller roll extrusion of 120～125 ℃ of excess temperatures 1～3 time.
Material after the roll extrusion is added fan-shaped mould, and the temperature of fan-shaped mould is controlled at 130～135 ℃, directed foaming.Be incubated 8～15 minutes, be cooled to room temperature then, take out goods, obtain negative poisson's ratio material, the aperture of its micropore is 80～150 μ m, and structure as shown in Figure 1.
Embodiment 4
With starch 69g, PCL 15g, glycerol 8g, sorbyl alcohol 5g, N, N ＇-dimethyl-N, N ＇-dinitrosoterephthalamine 1.5g, Cellmic C 121 1.5g, according to certain ratio extrude in screw extrusion press, without granulation, directly extrusion moulding.
Four district's temperature of middle layer and outer screw rod are respectively 90,110,120,100 ℃, and 100 ℃ of extrusion temperature, the initial temperature of pressure roller and mould also are 110 ℃, controlled temperature.
With outer screw rod extrusion foaming body bifurcated, add outer foam in the both sides of middle layer screw rod extrusion foaming body, through two roller roll extrusion of 120～125 ℃ of excess temperatures 1～3 time.
Material after the roll extrusion is added mould, and the temperature of mould is controlled at 130～135 ℃, directed foaming.Be incubated 8～15 minutes, be cooled to room temperature then, take out goods, obtain negative poisson's ratio material, the aperture of its micropore is 80～150 μ m, and structure as shown in Figure 1.
Embodiment 5
With starch 83g, glycerol 10g, sorbyl alcohol 5g, Cellmic C 121 2.0g, according to certain ratio, on high-speed mixer, mix earlier, in outer screw rod machine, extrude, without granulation, directly extrusion moulding.110 ℃ of extrusion temperature, the initial temperature of pressure roller and mould also are 110 ℃, controlled temperature.
In the screw extrusion press of middle layer, with polystyrene 98g, butane 2g mixes, extrusion foaming in screw rod, and the extrusion foaming body is through the two rollers of the heat of 80～85 ℃ of temperature.
The foam bifurcated that outer screw extrusion press is extruded, the both sides of the foam of extruding at middle layer screw rod machine add outer foam, through two roller roll extrusion of 125～130 ℃ of excess temperatures 1～3 time.
Material after the roll extrusion is added fan-shaped mould, and the temperature of fan-shaped mould is controlled at 130～135 ℃, directed foaming.Be incubated 8～15 minutes, be cooled to room temperature then, take out goods, obtain negative poisson's ratio material, the aperture of its micropore is 80～150 μ m, and structure as shown in Figure 1.
Embodiment 6
With starch 70g, PBS 15g, glycerol 8g, glycerine three acid anhydride ester 5g, Cellmic C 121 2.0g, according to certain ratio, on high-speed mixer, mix earlier, in outer screw extrusion press, extrude, without granulation, directly extrusion moulding.110 ℃ of extrusion temperature, the initial temperature of pressure roller and mould also are 110 ℃, controlled temperature.
In the screw extrusion press of middle layer, with polystyrene 98g, pentane 2g mixes, extrusion foaming in screw rod, and the extrusion foaming body is through the two rollers of the heat of 80～85 ℃ of temperature.
The foam bifurcated that outer screw rod machine is extruded, the both sides of the foam of extruding at the middle layer screw extrusion press add outer foam, through two roller roll extrusion of 125～130 ℃ of excess temperatures 1～3 time.
Material after the roll extrusion is added fan-shaped mould, and the temperature of fan-shaped mould is controlled at 130～135 ℃, directed foaming.Be incubated 8～15 minutes, be cooled to room temperature then, take out goods, obtain negative poisson's ratio material, the aperture of its micropore is 80～150 μ m, and structure as shown in Figure 1.
Embodiment 7
With starch 70g, PBS 15g, glycerol 8g, sorbyl alcohol 5g, Cellmic C 121 1.5g, N, N ＇-dimethyl-N, N ＇-dinitrosoterephthalamine 0.5g, proportionally preparation, extruding pelletization in screw extrusion press.Add a certain amount of above-mentioned particle according to required preparation foam size, 110～125 ℃ on even heating mould kept temperature 8～15 minutes.Be cooled to room temperature then and take out the goods object, as the middle layer, standby.
Above-mentioned sheet material of making or sheet material are placed in the another one fan-shaped mould, in this mould, foam sheet or sheet material are fixed in the middle of the mould, the mixture that the both sides of the sheet material in middle layer or sheet material is added above-mentioned prescription, the heating mould temperature is 130～135 ℃ rapidly, makes by expanded beads to be fan-shaped foaming rapidly in cavity.Be incubated 8～15 minutes, be cooled to room temperature then, take out goods.Be prepared into the foam material of the sandwich structure that comprises a middle layer and two layer structures.
The preparation of multilayer foams.In common die, foam under 70～150 ℃ of temperature of temperature, be prepared into well-regulated foam sheet or sheet material, be the middle layer;
The compound skin in the outside in this middle layer again.Be about to a middle layer and be placed in the fan-shaped mould, add the material in the prescription,, be prepared into and comprise a middle layer and an outer field composite bed at 70～150 ℃ of foamings.On the skin with this two-layer heat seal or bonding above-mentioned three layers of cystose preparing, prepare foam materials so then with five-layer structure.Increase multilayer again, can prepare the negative poisson's ratio material of multilayered structure according to present method.
Embodiment 8
With starch 83g, glycerol 10g, sorbyl alcohol 5g, Cellmic C 121 2.0g, according to certain ratio, on high-speed mixer, mix earlier, in outer screw extrusion press, extrude, without granulation, directly extrusion moulding.110 ℃ of extrusion temperature, the initial temperature of pressure roller and mould also are 110 ℃, controlled temperature.
In the screw extrusion press of middle layer, with polystyrene 98g, butane 2g mixes, extrusion foaming in screw rod, and the extrusion foaming body is through the two rollers of the heat of 80～85 ℃ of temperature.
The foam bifurcated that outer screw extrusion press is extruded, the both sides of the foam of extruding at the middle layer screw extrusion press add outer foam, through two roller roll extrusion of 125～130 ℃ of excess temperatures 1～3 time.
Material after the roll extrusion is added fan-shaped mould, and the temperature of fan-shaped mould is controlled at 130～135 ℃, directed foaming.Be incubated 8～15 minutes, be cooled to room temperature then, take out goods.Prepare the foam negative poisson's ratio material that comprises a middle layer and two layer structures.
The compound skin in the outside in this middle layer again.Be about to a middle layer and be placed in the fan-shaped mould, add the material in the prescription,, be prepared into and comprise a middle layer and an outer field composite bed at 70～150 ℃ of foamings.On the skin with this two-layer heat seal or bonding above-mentioned three layers of cystose preparing, prepare foam negative poisson's ratio material so then with five-layer structure.Increase multilayer again, can prepare according to present method.
Claims (15)
1. negative poisson's ratio material, it is characterized in that: this material is the sandwich that is prepared by natural polymer and/or synthesized polymer material, whipping agent 1, whipping agent 2 and softening agent, the foams of this material have microcosmic and are biflabellate composite structure, the middle layer of composite structure is the polygonal polynuclear plane of rule, the skin of composite structure is outside by the center, in the radial direction, gradually become the extended polynuclear plane, the skin of composite structure is the gradually long ordered arrangement of divergent shape, and the aperture of its micropore is 80～150 μ m;
Described whipping agent 1 is butane, pentane or their mixture;
Described whipping agent 2 is amine, azo class or their mixture;
Described natural macromolecular material is a kind of in starch, the Mierocrystalline cellulose or their mixture; Described synthesized polymer material is poly butylene succinate, poly-several lactones, poly(lactic acid), polyethylene, polypropylene, polystyrene or their any mixture.
2. negative poisson's ratio material according to claim 1 is characterized in that: the polygonal middle layer of the radial direction of described sandwich is pentagon or hexagon; The two outer field polynuclear planes up and down of sandwich are the extended hexagons.
3. negative poisson's ratio material according to claim 1 and 2 is characterized in that: described sandwich is by a skin, a middle layer, a skin, a middle layer, a skin, by that analogy, obtains the multi-layer compound structure material.
4. negative poisson's ratio material according to claim 1 and 2 is characterized in that: its vertical direction had swelling property when described negative poisson's ratio material had tension, and/or had when being squeezed and shrink and the mechanical property of extruding and compression property.
5. negative poisson's ratio material according to claim 3 is characterized in that: its vertical direction had swelling property when described negative poisson's ratio material had tension, and/or had when being squeezed and shrink and the mechanical property of extruding and compression property.
6. according to claim 1,2 or 5 described negative poisson's ratio materials, it is characterized in that: each component concentration of described negative poisson's ratio material is:
Natural polymer and/or synthesized polymer material 85.0wt%～90.0wt%
Whipping agent 1 0.5wt%～2.0wt%
Whipping agent 2 0.5wt%～2.0wt%
The softening agent surplus.
7. negative poisson's ratio material according to claim 3 is characterized in that: each component concentration of described negative poisson's ratio material is:
Natural polymer and/or synthesized polymer material 85.0wt%～90.0wt%
Whipping agent 1 0.5wt%～2.0wt%
Whipping agent 2 0.5wt%～2.0wt%
The softening agent surplus.
8. negative poisson's ratio material according to claim 4 is characterized in that: each component concentration of described negative poisson's ratio material is:
Natural polymer and/or synthesized polymer material 85.0wt%～90.0wt%
Whipping agent 1 0.5wt%～2.0wt%
Whipping agent 2 0.5wt%～2.0wt%
The softening agent surplus.
9. according to claim 1,7 or 8 described negative poisson's ratio materials, it is characterized in that: described softening agent is glycerol, sorbyl alcohol, propylene glycol, glycerine three acid anhydride esters, glycerine list acid anhydride ester or their mixture.
10. negative poisson's ratio material according to claim 6 is characterized in that: described softening agent is glycerol, sorbyl alcohol, propylene glycol, glycerine three acid anhydride esters, glycerine list acid anhydride ester or their mixture.
11. negative poisson's ratio material according to claim 1 is characterized in that: described amine is N, N '-dimethyl-N, N '-dinitrosoterephthalamine; The azo class is a Cellmic C 121.
12. the preparation method according to each described negative poisson's ratio material of claim 1～11 is prepared by second time of foaming method or screw rod extrusion foaming method, it is characterized in that the prescription of material and content are:
Natural polymer and/or synthesized polymer material 85.0wt%～90.0wt%
Whipping agent 1 0.5wt%～2.0wt%;
Whipping agent 2 0.5wt%～2.0wt%;
The softening agent surplus;
A. the second time of foaming method may further comprise the steps:
(1) preparation of homogeneous phase microcellular foam material
Raw material in the above-mentioned prescription is proportionally mixed, and high-speed stirring mixes, directly put into mould, perhaps in two rollers, make sheet material and be placed on again in the mould, under 70～150 ℃ of temperature, foam, be prepared into well-regulated foam sheet or sheet material, as the middle layer;
(2) preparation of directed microcellular foam material
Raw material in the above-mentioned prescription proportionally mixed being placed in the fan-shaped mould, foamable on fan-shaped mould remains on more than 125 ℃ temperature, makes its directed foaming, makes the sheet material or the sheet material of directed foaming, as skin;
(3) preparation of negative poisson's ratio material
Sheet material that step (1) is obtained or sheet material are combined with each other in the middle of being placed on sheet material that step (2) obtains or sheet material, be the sheet material or the sheet material of two-layer step (2), the centre sandwiches the sheet material or the sheet material of one deck step (1), form microtexture and be biflabellate three-decker, direct heat lumps together then, perhaps use sizing agent to bond together, be prepared into the foam sheet or the board product of negative poisson's ratio material; Or
Directly sheet material or the sheet material that step (1) is obtained is put into the segmental mould, put into the material of prescription again on the both sides up and down of this sheet material or sheet material, directly, be prepared into the foam sheet or the board product of negative poisson's ratio material at the directed foaming in the both sides up and down in middle layer; Or
B. screw rod extrusion foaming method may further comprise the steps:
Select the screw rod of two kinds of different bores, according to the cell size of foam material, the requirement difference of density size, the temperature of the extruder head of the screw rod of control forcing machine and the temperature of fan-shaped mould, wherein the temperature of the extruder head of screw rod is 70～125 ℃, the temperature of fan-shaped mould is 130～135 ℃; Extrude outer screw rod bore greater than the middle layer;
Will be by the middle layer foam that screw rod is extruded through the two rollers of 80～125 ℃ heat, the outer material of extruding by screw rod is the two rollers of heat outside and then, at outer material through the material both sides, middle layer behind the overheated pair of roller are compound, again through the two rollers of the heat of 125～130 ℃ of excess temperatures, directed foaming in mould then is prepared into the foam sheet or the board product of negative poisson's ratio material.
13. method according to claim 12 is characterized in that: four sections temperature of the material extrusion screw rod in described middle layer all are 70～i20 ℃; Four of screw rod sections temperature all were 110～120 ℃ when outer field material was extruded.
14. method according to claim 12 is characterized in that: according to the preparation method of the homogeneous phase microcellular foam material of claim 12, preparation middle layer and skin; At the compound skin of the both sides in middle layer difference, be prepared into and comprise a middle layer and two outer field composite beds, then with their heat seals or be bonded together, a compound middle layer and a skin on a skin again, then with their heat seals or be bonded together, by that analogy, obtain the foam sheet or the sheet material of the negative poisson's ratio material of multi-layer microporous structure.
15. the purposes according to each described negative poisson's ratio material of claim 1～11 is characterized in that: this material uses as the material of composite sheet.
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| CN102175512B (en) * | 2010-12-31 | 2013-01-30 | 清华大学 | Test piece with negative Poisson ratio performance |
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