CN102827445A - Water-soluble core mold material for forming filament-wound case and preparation method of water-soluble core mold material - Google Patents
Water-soluble core mold material for forming filament-wound case and preparation method of water-soluble core mold material Download PDFInfo
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Abstract
The invention relates to a water-soluble core mold material for forming a filament-wound case and a preparation method of the water-soluble core mold material. The water-soluble core mold material for forming the filament-wound case comprises composite binder aqueous solution and core mold packing, and the composite binder aqueous solution comprises polyvinyl pyrrolidone binder aqueous solution and polyvinyl alcohol binder aqueous solution. The polyvinyl pyrrolidone binder aqueous solution accounting for 20-80Wt% of the total mass of the composite binder aqueous solution is mixed with the polyvinyl alcohol binder aqueous solution to prepare the composite binder aqueous solution. The addition quantity of the water-soluble high-polymer binder aqueous solution is 0.05-0.5 time of the weight of the core mold packing. The preparation method includes steps of preparing the polyvinyl pyrrolidone binder aqueous solution; preparing the polyvinyl alcohol binder aqueous solution; preparing the composite binder aqueous solution; preparing the packing; mixing the materials; filling and forming; drying and solidifying; and demoulding and machining. The density and the compressive strength of a core mold prepared by the method can be adjusted according to service conditions, and the core mold is good in temperature resistance, room-temperature water-soluble collapsibility and fracture toughness, and is free of environmental pollution.
Description
Technical field
The present invention relates to a kind of fiber winding shell moulding and use water-soluble core mould, be specifically related to a kind of fiber winding shell moulding with water-soluble core mould material and preparation method.
Background technology
In the polymer matrix composites manufacturing processed; Usually select for use metal as moulding stock; Because metal has high thermal conductivity and good rigidity, and metal can process the surface of good roughness, and the matrix material that produces so also has good surface roughness.But also there are some shortcomings in metal as moulding stock.For example, for large-size components, mold weight is difficult to operation too greatly; In addition, the processing conditions of processing a large-scale metal die requirement is higher, length consuming time, and also cost is also higher.In full tree resin-based composite winding process, the traditional metal mould can't satisfy requirements such as its global formation demoulding, HS, therefore is badly in need of the new core material of exploitation to adapt to the development of processing of polymer matrix composites technology.
Water-soluble polymer is the macromolecular compound with hydrophilic group, can dissolving in water or swelling and form solution or dispersion liquid.The wetting ability of water-soluble polymer comes from the hydrophilic radical that contains in the molecule, and common hydrophilic radical has hydroxyl, carboxyl, carboxamido-group, amido, ether etc.The water-soluble core mould that adopts water-soluble polymer to process as sticker owing to have defeated and dispersed characteristic, the good heat-resisting property of the water of chance, just progressively is employed in the matrix material field of making.
At present, the water-soluble binder that the processing of polymer matrix composites core is commonly used has Z 150PH and Vinylpyrrolidone polymer.Be easy to moulding though use polyvinyl alcohol adhesive to make core; But this water-soluble polymer second-order transition temperature is lower; Thermostability is relatively poor, core with the polymer matrix composites regelate after (temperature is above 150 ℃), polyvinyl alcohol adhesive has phenomenons such as jaundice, sintering; Make the water-soluble collapsibility variation of core material or do not possess water-soluble collapsibility, increased the whole demoulding difficulty of core.Vinylpyrrolidone polymer is compared with Z 150PH, has the characteristics of second-order transition temperature height (can reach 190 ℃), good water solubility.For example, application number be 200910308993.8 one Chinese patent application just disclose a kind of Vinylpyrrolidone polymer as the polymer matrix composites of water-soluble binder with water-soluble moulding stock and make water-soluble mould method.Because it is bigger to constitute the molecular chain rigidity of Vinylpyrrolidone polymer, adopt separately the Vinylpyrrolidone polymer sticker make large-scale, when light fibre twines housing moulding core, core toughness is relatively poor, adds at moulding, machine, is easy to damage core in the transportation.Therefore, a kind of water-soluble core mould that has both excellent water-soluble collapsibility and fracture toughness property of preparation has major application value in the fiber winding shell moulding process.
Summary of the invention
It is poor to the objective of the invention is to the water-soluble collapsibility of water-soluble core mould that exists in the prior art; Second-order transition temperature is low, and fragility is big, does not satisfy the problem of global formation, demoulding requirement; Provide a kind of water-soluble collapsibility good; Second-order transition temperature is high, and fracture toughness property is good, and is applicable to that the fiber winding shell moulding is with water-soluble core mould material and preparation method.
The water-soluble core mould material is used in a kind of fiber winding shell moulding provided by the present invention, comprises high molecular weight water soluble polymer adhesive solution and core filler.The high molecular weight water soluble polymer adhesive solution is the compound binding agent aqueous solution that comprises the Vinylpyrrolidone polymer adhesive solution and the polyvinyl alcohol adhesive aqueous solution; Wherein the concentration of Vinylpyrrolidone polymer adhesive solution is 10～50Wt.%, and the concentration of the polyvinyl alcohol adhesive aqueous solution is 5～20Wt.%.The compound binding agent aqueous solution accounts for 20～80Wt.% mixed preparing of total mass by the Vinylpyrrolidone polymer adhesive solution.And the add-on of high molecular weight water soluble polymer adhesive solution is 0.05～0.5 times of core filler weight.
The core filler is that 45～150 purpose silica sands and 50～200 purpose hollow glass micropearls are accounted for 10～90Wt.% of total mass by silica sand is mixed.
The present invention also provides the preparation method of a kind of fiber winding shell moulding with water-soluble core mould, may further comprise the steps:
(1) preparation Vinylpyrrolidone polymer adhesive solution: in water, add the polyvinylpyrrolidonepowder powder of 10～50Wt.%, fully stir, and it is dissolved fully, make the aqueous solution of Vinylpyrrolidone polymer sticker;
(2) the preparation polyvinyl alcohol adhesive aqueous solution: in water, add the pva powder of 5～20Wt.%, fully stir, and it is dissolved fully, make the aqueous solution of polyvinyl alcohol adhesive;
(3) the preparation compound binding agent aqueous solution: will mix by 20～80Wt.% that the Vinylpyrrolidone polymer adhesive solution accounts for total mass with the polyvinyl alcohol adhesive aqueous solution for preparing through step (2) through the Vinylpyrrolidone polymer adhesive solution that step (1) prepares; Fully stir; And it is mixed, make the aqueous solution of compound binding agent;
(4) preparation filler: 45～150 purpose silica sands are mixed by 10～90Wt.% that silica sand accounts for total mass with 50～200 purpose hollow glass micropearls, fully stir, and it is mixed, make the core filler; (5) batch mixing: will join through the compound binding agent aqueous solution that step (3) prepare in the core filler that step (4) prepares; The add-on of the compound binding agent aqueous solution is 0.05～0.5 times of filler weight; Use stirrer or other blending device that the compound that obtains is carried out thorough mixing; Make the core slurry, mixing time is 10～30min;
(6) filling moulding: will be loaded into through the core slurry that step (5) mix in the mould and also use the press compacting, the pressure of core slurry in compacting process is 1～5MPa, and the dwell time is 2～10min;
(7) dry solidification: the core after the above-mentioned filling moulding is put into baking oven carry out drying and dehydrating, it is 0.5～4 ℃/min that room temperature rises to the holding temperature temperature rise rate, and holding temperature is 110～140 ℃, and soaking time is 5～50h;
(8) form removal and machine add: disassemble the mandrel molding mould behind the dry solidification, carry out mechanical workout for the core that shape requirement is arranged.
The present invention compared with prior art has the following advantages:
(1) use the mixed aqueous solution of Z 150PH and Vinylpyrrolidone polymer to make sticker; Because Z 150PH molecular chain snappiness is better; Still have good fracture toughness property behind the core dry solidification, dismounting and the carrying of follow-up core of being convenient to the mandrel molding mould add with machine.
(2) use the mixed aqueous solution of Z 150PH and Vinylpyrrolidone polymer to make sticker; Because the Vinylpyrrolidone polymer temperature tolerance is better; After prepared core solidifies with polymer matrix composites once more; Still keep good water-soluble collapsibility, satisfy the whole demoulding requirement of core, and the water-soluble defeated and dispersed of core can carry out in room temperature water.
(3) use the mixed aqueous solution of Z 150PH and Vinylpyrrolidone polymer to make sticker, prepared water-soluble core mould has the good high-temperature mechanical property, can satisfy the cure process requirement of each temperature section resin matrix.
(4) filler that uses of present method can change according to core density and ultimate compression strength design requirements, and prepared water-soluble core mould dimensional precision is high, and thermal expansivity is little, reaches the requirement of mating with the institute composite material structural member of producing.
(5) employed starting material do not have toxicity in present method, can not bring problem of environmental pollution yet, and filler can reuse.Have advantages such as cost is low, simple to operate, non-environmental-pollution, be applicable to suitability for industrialized production.
Embodiment
Explain further details in the face of the present invention down.The water-soluble core mould preparation method is used in a kind of fiber winding shell moulding, and the preparing method's of this water-soluble core mould concrete operations step is following:
(1) preparation Vinylpyrrolidone polymer adhesive solution: in water, add the polyvinylpyrrolidonepowder powder of 10～50Wt.%, fully stir, and it is dissolved fully, make the aqueous solution of Vinylpyrrolidone polymer sticker;
(2) the preparation polyvinyl alcohol adhesive aqueous solution: in water, add the pva powder of 5～20Wt.%, fully stir, and it is dissolved fully, make the aqueous solution of polyvinyl alcohol adhesive;
(3) the preparation compound binding agent aqueous solution: will mix by 20～80Wt.% that the Vinylpyrrolidone polymer adhesive solution accounts for total mass with the polyvinyl alcohol adhesive aqueous solution for preparing through step (2) through the Vinylpyrrolidone polymer adhesive solution that step (1) prepares; Fully stir; And it is mixed, make the aqueous solution of compound binding agent;
(4) preparation filler: 45～150 purpose silica sands are mixed by 10～90Wt.% that silica sand accounts for total mass with 50～200 purpose hollow glass micropearls, fully stir, and it is mixed, make the core filler;
(5) batch mixing: will join through the compound binding agent aqueous solution that step (3) prepare in the core filler that step (4) prepares; The add-on of the compound binding agent aqueous solution is 0.05～0.5 times of filler weight; Use stirrer or other blending device that the compound that obtains is carried out thorough mixing; Make the core slurry, mixing time is 10～30min;
(6) filling moulding: will be loaded into through the core slurry that step (5) mix in the mould and also use the press compacting, the pressure of core slurry in compacting process is 1～5MPa, and the dwell time is 2～10min;
(7) dry solidification: the core after the above-mentioned filling moulding is put into baking oven carry out drying and dehydrating, it is 0.5～4 ℃/min that room temperature rises to the holding temperature temperature rise rate, and holding temperature is 110～140 ℃, and soaking time is 5～50h;
(8) form removal and machine add: disassemble the mandrel molding mould behind the dry solidification, carry out mechanical workout for the core that shape requirement is arranged.
Embodiment 1
Adopt PVP K30 and PVA 04-86 to make Vinylpyrrolidone polymer and polyvinyl alcohol adhesive respectively, PVP K30 presses the concentration preparation of 20Wt.%, and PVA 04-86 presses the concentration preparation of 10Wt.%; Vinylpyrrolidone polymer adhesive solution and the polyvinyl alcohol adhesive aqueous solution are accounted for the 20Wt.% mixing for standby use of total mass by the Vinylpyrrolidone polymer adhesive solution; Weighing 8Kg silica sand and 12Kg hollow glass micropearl, the back that stirs adds the compound binding agent 3Kg for preparing, and on mixer, stirs 10min; Pack in the mandrel molding mould and use the press compacting; Pressure is 2MPa, and the dwell time is 5min, puts into baking oven then and rises to 110 ℃ by 1 ℃/min temperature rise rate; Insulation 30h; Dismounting mandrel molding frock is carried out machine by the profile design requirements to mandrel surface again and is added behind the core dry solidification, and machine promptly makes water-soluble core mould after adding completion.
Embodiment 2
Adopt PVP K30 and PVA 0588 to make Vinylpyrrolidone polymer and polyvinyl alcohol adhesive respectively, PVPK30 presses the concentration preparation of 40Wt.%, and PVA 0588 presses the concentration preparation of 5Wt.%; Vinylpyrrolidone polymer adhesive solution and the polyvinyl alcohol adhesive aqueous solution are accounted for the 50Wt.% mixing for standby use of total mass by the Vinylpyrrolidone polymer adhesive solution; Weighing 10Kg silica sand and 10Kg hollow glass micropearl, the back that stirs adds the compound binding agent 2Kg for preparing, and on mixer, stirs 30min; Pack in the mandrel molding mould and use the press compacting; Pressure is 4MPa, and the dwell time is 2min, puts into baking oven then and rises to 110 ℃ by 0.5 ℃/min temperature rise rate; Insulation 20h; Dismounting mandrel molding frock is carried out machine by the profile design requirements to mandrel surface again and is added behind the core dry solidification, and machine promptly makes water-soluble core mould after adding completion.
Embodiment 3
Adopt PVP K30 and PVA 0588 to make Vinylpyrrolidone polymer and polyvinyl alcohol adhesive respectively, PVPK30 presses the concentration preparation of 50Wt.%, and PVA 0588 presses the concentration preparation of 10Wt.%; Vinylpyrrolidone polymer adhesive solution and the polyvinyl alcohol adhesive aqueous solution are accounted for the 80Wt.% mixing for standby use of total mass by the Vinylpyrrolidone polymer adhesive solution; Weighing 2Kg silica sand and 18Kg hollow glass micropearl, the back that stirs adds the compound binding agent 3.5Kg for preparing, and on mixer, stirs 20min; Pack in the mandrel molding mould and use the press compacting; Pressure is 5MPa, and the dwell time is 10min, puts into baking oven then and rises to 120 ℃ by 2 ℃/min temperature rise rate; Insulation 40h; Dismounting mandrel molding frock is carried out machine by the profile design requirements to mandrel surface again and is added behind the core dry solidification, and machine promptly makes water-soluble core mould after adding completion.
Embodiment 4
Adopt PVP K90 and PVA 04-86 to make Vinylpyrrolidone polymer and polyvinyl alcohol adhesive respectively, PVP K90 presses the concentration preparation of 10Wt.%, and PVA 04-86 presses the concentration preparation of 15Wt.%; Vinylpyrrolidone polymer adhesive solution and the polyvinyl alcohol adhesive aqueous solution are accounted for the 40Wt.% mixing for standby use of total mass by the Vinylpyrrolidone polymer adhesive solution; Weighing 18Kg silica sand and 2Kg hollow glass micropearl, the back that stirs adds the compound binding agent 4Kg for preparing, and on mixer, stirs 15min; Pack in the mandrel molding mould and use the press compacting; Pressure is 1MPa, and the dwell time is 8min, puts into baking oven then and rises to 130 ℃ by 1 ℃/min temperature rise rate; Insulation 45h; Dismounting mandrel molding frock is carried out machine by the profile design requirements to mandrel surface again and is added behind the core dry solidification, and machine promptly makes water-soluble core mould after adding completion.
Embodiment 5
Adopt PVP K30 and PVA 0588 to make Vinylpyrrolidone polymer and polyvinyl alcohol adhesive respectively, PVPK30 presses the concentration preparation of 30Wt.%, and PVA 0588 presses the concentration preparation of 20Wt.%; Vinylpyrrolidone polymer adhesive solution and the polyvinyl alcohol adhesive aqueous solution are accounted for the 60Wt.% mixing for standby use of total mass by the Vinylpyrrolidone polymer adhesive solution; Weighing 14Kg silica sand and 6Kg hollow glass micropearl, the back that stirs adds the compound binding agent 3Kg for preparing, and on mixer, stirs 15min; Pack in the mandrel molding mould and use the press compacting; Pressure is 3MPa, and the dwell time is 6min, puts into baking oven then and rises to 140 ℃ by 4 ℃/min temperature rise rate; Insulation 5h; Dismounting mandrel molding frock is carried out machine by the profile design requirements to mandrel surface again and is added behind the core dry solidification, and machine promptly makes water-soluble core mould after adding completion.
Embodiment 6
Adopt PVP K30 and PVA 0588 to make Vinylpyrrolidone polymer and polyvinyl alcohol adhesive respectively, PVPK30 presses the concentration preparation of 20Wt.%, and PVA 0588 presses the concentration preparation of 5Wt.%; Vinylpyrrolidone polymer adhesive solution and the polyvinyl alcohol adhesive aqueous solution are accounted for the 70Wt.% mixing for standby use of total mass by the Vinylpyrrolidone polymer adhesive solution; Weighing 6Kg silica sand and 14Kg hollow glass micropearl, the back that stirs adds the compound binding agent 2Kg for preparing, and on mixer, stirs 20min; Pack in the mandrel molding mould and use the press compacting; Pressure is 3MPa, and the dwell time is 4min, puts into baking oven then and rises to 120 ℃ by 3 ℃/min temperature rise rate; Insulation 10h; Dismounting mandrel molding frock is carried out machine by the profile design requirements to mandrel surface again and is added behind the core dry solidification, and machine promptly makes water-soluble core mould after adding completion.
Above-mentioned is to specify of the present invention, and the present invention is not limited to this.Water-soluble core mould of the present invention also can be applicable to other composite material process plannings such as lay, hand paste.And the core filler among the present invention also can adopt ceramics powders such as aluminium sesquioxide, titanium oxide to replace.Protection scope of the present invention is limited its claims.
Claims (3)
1. the water-soluble core mould material is used in a fiber winding shell moulding; Comprise high molecular weight water soluble polymer adhesive solution and core filler; It is characterized in that: said high molecular weight water soluble polymer adhesive solution is the compound binding agent aqueous solution that comprises the Vinylpyrrolidone polymer adhesive solution and the polyvinyl alcohol adhesive aqueous solution; Wherein the concentration of Vinylpyrrolidone polymer adhesive solution is 10～50Wt.%, and the concentration of the polyvinyl alcohol adhesive aqueous solution is 5～20Wt.%; The compound binding agent aqueous solution accounts for 20～80Wt.% mixed preparing of total mass by the Vinylpyrrolidone polymer adhesive solution; And the add-on of said high molecular weight water soluble polymer adhesive solution is 0.05～0.5 times of core filler weight.
2. water-soluble core mould material according to claim 1 is characterized in that, said core filler is that 45～150 purpose silica sands and 50～200 purpose hollow glass micropearls are accounted for 10～90Wt.% of total mass by silica sand is mixed.
3. a fiber winding shell moulding is characterized in that with the preparation method of water-soluble core mould the operation steps of this method is following:
(1) preparation Vinylpyrrolidone polymer adhesive solution: in water, add the polyvinylpyrrolidonepowder powder of 10～50Wt.%, fully stir, and it is dissolved fully, make the aqueous solution of Vinylpyrrolidone polymer sticker;
(2) the preparation polyvinyl alcohol adhesive aqueous solution: in water, add the pva powder of 5～20Wt.%, fully stir, and it is dissolved fully, make the aqueous solution of polyvinyl alcohol adhesive;
(3) the preparation compound binding agent aqueous solution: will mix by 20～80Wt.% that the Vinylpyrrolidone polymer adhesive solution accounts for total mass with the polyvinyl alcohol adhesive aqueous solution for preparing through step (2) through the Vinylpyrrolidone polymer adhesive solution that step (1) prepares; Fully stir; And it is mixed, make the aqueous solution of compound binding agent;
(4) preparation filler: 45～150 purpose silica sands are mixed by 10～90Wt.% that silica sand accounts for total mass with 50～200 purpose hollow glass micropearls, fully stir, and it is mixed, make the core filler;
(5) batch mixing: will join through the compound binding agent aqueous solution that step (3) prepare in the core filler that step (4) prepares; The add-on of the compound binding agent aqueous solution is 0.05～0.5 times of filler weight; Use stirrer or other blending device that the compound that obtains is carried out thorough mixing; Make the core slurry, mixing time is 10～30min;
(6) filling moulding: will be loaded into through the core slurry that step (5) mix in the mould and also use the press compacting, the pressure of core slurry in compacting process is 1～5MPa, and the dwell time is 2～10min;
(7) dry solidification: the core after the above-mentioned filling moulding is put into baking oven carry out drying and dehydrating, it is 0.5～4 ℃/min that room temperature rises to the holding temperature temperature rise rate, and holding temperature is 110～140 ℃, and soaking time is 5～50h;
(8) form removal and machine add: disassemble the mandrel molding mould behind the dry solidification, carry out mechanical workout for the core that shape requirement is arranged.
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