CN104672846A - Glass fiber reinforced polycarbonate (PC) composite material and preparation method thereof - Google Patents
Glass fiber reinforced polycarbonate (PC) composite material and preparation method thereof Download PDFInfo
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- CN104672846A CN104672846A CN201310625121.0A CN201310625121A CN104672846A CN 104672846 A CN104672846 A CN 104672846A CN 201310625121 A CN201310625121 A CN 201310625121A CN 104672846 A CN104672846 A CN 104672846A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a glass fiber reinforced polycarbonate (PC) composite material. The glass fiber reinforced PC composite material is prepared from the following components in parts by weight: 100 parts of PC resin, 3-20 parts of polyethylene terephthalate glycol (PETG) resin, 15-50 parts of glass fiber, 1-8 parts of toughening agents, 0.5-12 parts of environment-friendly flame retardants, 0.5-2 parts of coupling agents, 1.0-4.0 parts of flow modifiers and 0.3-1.0 part of antioxidants. A preparation method comprises the following steps: uniformly mixing 100 parts of PC resin, 3-20 parts of PETG resin, 1-8 parts of toughening agents, 0.5-12 parts of environment-friendly flame retardants, 0.5-2 parts of coupling agents, 1.0-4.0 parts of flow modifiers and 0.3-1.0 part of antioxidants, adding the obtained mixed materials and 15-50 parts of glass fiber to a screw extruder and carrying out extrusion pelletizing, and carrying out stranding pelletizing to prepare the glass fiber reinforced PC composite material. The composite material has the characteristics of easiness in forming, good processed surface quality, no floating fibers, environment-friendly flame retardance, high gloss and high flowability.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to the high flowing in a kind of environmentally friendly flame-retarding high-lustre pool glass fiber reinforced polycarbonate matrix material and preparation method thereof.
Background technology
Polycarbonate (PC) because of its physical and mechanical properties excellent, excellent in cushion effect, good electrical property, features such as good stability of the dimension and be widely used in each fields of social life such as electronic apparatus, building materials, packaging, automotive industry, that current production rate is maximum, one of most widely used polymkeric substance.Glass fiber reinforced polycarbonate material significantly can improve the mechanical property of polycarbonate material, reduce the thermal expansivity of material, improve its stress cracking performance, improve fatigue resistance, may be used for the materials application such as substitution of Al, zinc and manufacture various component in the Industrial products such as electric, instrument, telecommunications.
But polycarbonate viscosity is large, moulding processability is poor, and it is poorer to add glass fibre post-treatment mobility, very easily occurs glass emergence on the surface phenomenon, has a strong impact on the apparent mass of goods.On the other hand, because the thermal conductivity of glass fibre is large, and " wick effect " etc. causes the flame retardant properties of PC material to worsen, traditional bromide fire retardant good flame retardation effect, but do not meet environmental requirement containing a large amount of halogen, phosphorus flame retardant addition is large, affects material property.
Summary of the invention
For the defect of prior art, the object of this invention is to provide the high flowing in a kind of environmentally friendly flame-retarding high-lustre pool glass fiber reinforced polycarbonate matrix material.
Another object of the present invention is to provide a kind of preparation method of above-mentioned glass fiber reinforced polycarbonate matrix material.
To achieve these goals, technical scheme of the present invention is as follows:
The invention provides a kind of glass fiber reinforced polycarbonate matrix material, be made up of the component comprising following weight part:
Described PC resin is bisphenol A polycarbonate, and melting index is 13 ~ 30g/10min.
Described glass fibre is short glass fiber, and diameter is 6 ~ 18 μm, is preferably 7 ~ 11 μm.
Described toughner be selected from ethylene-methyl acrylate copolymer (EMA), maleic anhydride grafted linear low density polyethylene (LLDPE-g-MAH) or MBS terpolymer (MBS) one or more.
Described environmental protection fire retarding agent be selected from polyphosphonates, poly-phosphine-carbonate resin or organosilicon sulfonic acid salt one or more.
Described coupling agent be selected from vinyltriethoxysilane (KH-151), γ-aminopropyl triethoxysilane (KH-550), γ-glycidyl ether oxygen propyl trimethoxy silicane (KH-560) or atactic styrene-maleic anhydride copolymer (SMA) one or more.
Described flow ability modifying agent be selected from fatty acid ester, cyclic butylene terephthalate (CBT), PE wax or ethylene bis-fatty acid amides (TAF) one or more.
Described oxidation inhibitor is selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester (antioxidant 1010), β-(3,5-di-tert-butyl-hydroxy phenyl) one or more in propionic acid positive octadecanol ester (antioxidant 1076), three [2.4-di-tert-butyl-phenyl] phosphorous acid ester (irgasfos 168) or two (2,4-DTBP) pentaerythritol diphosphites (oxidation inhibitor 626).
Present invention also offers a kind of preparation method of above-mentioned glass fiber reinforced polycarbonate matrix material, comprise the following steps:
100 parts of PC resins, 3 ~ 20 parts of PETG resins, 1 ~ 8 part of toughner, 0.5 ~ 12 part of environmental protection fire retarding agent, 0.5 ~ 2 part of coupling agent, 1.0 ~ 4.0 parts of flow ability modifying agents and 0.3 ~ 1.0 part of oxidation inhibitor are mixed, the mixture of gained is added screw extrusion press extruding pelletization together with 15 ~ 50 parts of glass fibre, and tie rod pelletizing prepares glass fiber reinforced polycarbonate matrix material.
Described mixing is carried out in high mixer, and high mixer rotating speed is 500 ~ 700rpm, and mixing temperature is 60 ~ 90 DEG C, and mixing time is 3 ~ 8min.
Described screw extrusion press is twin screw extruder, is 220 ~ 240 DEG C respectively, 230 ~ 250 DEG C, 250 ~ 270 DEG C, 260 ~ 275 DEG C, 260 ~ 270 DEG C, engine speed 20 ~ 50 hertz from spout to the extrusion temperature of extruder die head.
The present invention compared with the existing technology, has the following advantages and beneficial effect:
Glass fiber reinforced polycarbonate matrix material provided by the invention, effectively overcome that glass fiber reinforced polyester carbonic ether matrix material glass emergence on the surface surface quality is poor, the large processing fluidity of viscosity is bad, conventional flame retardant addition greatly, not environmentally, the bad shortcoming of material property, obtain and be a kind ofly easy to shaping, machined surface quality, without the high flowing in floating fine environmentally friendly flame-retarding high-lustre pool glass fiber reinforced polycarbonate matrix material.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed explanation.
PC resin used is below bisphenol A polycarbonate, and melting index is 13 ~ 30g/10min.
Glass fibre used is below short glass fiber, and diameter is 6 ~ 18 μm, is preferably 7 ~ 11 μm.
Embodiment 1
Each ingredients weight parts content:
Prepare burden by above-mentioned weight part content, PC resin, PETG resin, toughner, environmental protection fire retarding agent, coupling agent, flow ability modifying agent, it is 60 DEG C that oxidation inhibitor drops into mixing temperature in high-speed mixer, mixing time is 8min, mixing rate is 500rmp, at a high speed after mixing, blanking is to forcing machine hopper, glass fibre adds in forcing machine glass fiber opening, control each district temperature (from spout to extruder die head) and be respectively 240 DEG C, 250 DEG C, 270 DEG C, 275 DEG C, 265 DEG C, engine speed 20 hertz, through twin screw extruder extruding pelletization, tie rod pelletizing prepares glass fiber reinforced polycarbonate matrix material.
The each performance of sample of the present embodiment is respectively: tensile strength 86.3MPa, flexural strength 147.6MPa, simply supported beam notched Izod impact strength 16KJ/m
2, melting index 28.5g/10min, flame retardant rating V-0, specimen surface is without floating fibre, and surface-brightening is smooth.It is poor that the present embodiment sample overcomes glass emergence on the surface surface quality, the shortcoming of the large processing insufficient formability of viscosity, obtained the high gloss environment-protection flame-proof fiberglass reinforced polycarbonate matrix material that the good surface quality of processing fluidity is good.
Embodiment 2
Each ingredients weight parts content:
Prepare burden by above-mentioned weight part content, PC resin, PETG resin, toughner, environmental protection fire retarding agent, coupling agent, flow ability modifying agent, it is 70 DEG C that oxidation inhibitor drops into mixing temperature in high-speed mixer, mixing time is 5min, mixing rate is 600rmp, at a high speed after mixing, blanking is to forcing machine hopper, glass fibre adds in forcing machine glass fiber opening, control each district temperature (from spout to extruder die head) and be respectively 230 DEG C, 240 DEG C, 260 DEG C, 268 DEG C, 270 DEG C, engine speed 30 hertz, through twin screw extruder extruding pelletization, tie rod pelletizing prepares glass fiber reinforced polycarbonate matrix material.
The each performance of sample of the present embodiment is respectively: tensile strength 92MPa, flexural strength 152.3MPa, simply supported beam notched Izod impact strength 14KJ/m
2, melting index 28.7g/10min, flame retardant rating V-1, specimen surface is without floating fibre, and surface-brightening is smooth.It is poor that the present embodiment sample overcomes glass emergence on the surface surface quality, the shortcoming of the large processing insufficient formability of viscosity, obtained the high gloss environment-protection flame-proof fiberglass reinforced polycarbonate matrix material that the good surface quality of processing fluidity is good.
Embodiment 3
Each ingredients weight parts content:
Prepare burden by above-mentioned weight part content, PC resin, PETG resin, toughner, environmental protection fire retarding agent, coupling agent, flow ability modifying agent, it is 90 DEG C that oxidation inhibitor drops into mixing temperature in high-speed mixer, mixing time is 3min, mixing rate is 700rmp, at a high speed after mixing, blanking is to forcing machine hopper, glass fibre adds in forcing machine glass fiber opening, control each district temperature (from spout to extruder die head) and be respectively 230 DEG C, 240 DEG C, 260 DEG C, 268 DEG C, 270 DEG C, engine speed 40 hertz, through twin screw extruder extruding pelletization, tie rod pelletizing prepares glass fiber reinforced polycarbonate matrix material.
The each performance of sample of the present embodiment is respectively: tensile strength 98.5MPa, flexural strength 162.7MPa, simply supported beam notched Izod impact strength 17.3KJ/m
2, melting index 38.2g/10min, flame retardant rating V-0, specimen surface is without floating fibre, and surface-brightening is smooth.It is poor that the present embodiment sample overcomes glass emergence on the surface surface quality, the shortcoming of the large processing insufficient formability of viscosity, obtained the high gloss environment-protection flame-proof fiberglass reinforced polycarbonate matrix material that the good surface quality of processing fluidity is good.
Embodiment 4
Each ingredients weight parts content:
Prepare burden by above-mentioned weight part content, PC resin, PETG resin, toughner, environmental protection fire retarding agent, coupling agent, flow ability modifying agent, it is 90 DEG C that oxidation inhibitor drops into mixing temperature in high-speed mixer, mixing time is 6min, mixing rate is that 600rmp blanking is to forcing machine hopper, glass fibre adds in forcing machine glass fiber opening, control each district temperature (from spout to extruder die head) and be respectively 220 DEG C, 230 DEG C, 250 DEG C, 260 DEG C, 260 DEG C, engine speed 50 hertz, through twin screw extruder extruding pelletization, tie rod pelletizing prepares glass fiber reinforced polycarbonate matrix material.
The each performance of sample of the present embodiment is respectively: tensile strength 115.7MPa, flexural strength 188.3MPa, simply supported beam notched Izod impact strength 15.9KJ/m
2, melting index 28.2g/10min, flame retardant rating V-0, specimen surface is without floating fibre, and surface-brightening is smooth.It is poor that the present embodiment sample overcomes glass emergence on the surface surface quality, the shortcoming of the large processing insufficient formability of viscosity, obtained the high gloss environment-protection flame-proof fiberglass reinforced polycarbonate matrix material that the good surface quality of processing fluidity is good.
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (10)
1. a glass fiber reinforced polycarbonate matrix material, is characterized in that: be made up of the component comprising following weight part:
2. glass fiber reinforced polycarbonate matrix material according to claim 1, is characterized in that: described PC resin is bisphenol A polycarbonate, and melting index is 13 ~ 30g/10min.
3. glass fiber reinforced polycarbonate matrix material according to claim 1, is characterized in that: described glass fibre is short glass fiber, and diameter is 6 ~ 18 μm, is preferably 7 ~ 11 μm.
4. glass fiber reinforced polycarbonate matrix material according to claim 1, is characterized in that: described toughner be selected from ethylene-methyl acrylate copolymer, maleic anhydride grafted linear low density polyethylene or MBS terpolymer one or more.
5. glass fiber reinforced polycarbonate matrix material according to claim 1, is characterized in that: described environmental protection fire retarding agent be selected from polyphosphonates, poly-phosphine-carbonate resin or organosilicon sulfonic acid salt one or more.
6. glass fiber reinforced polycarbonate matrix material according to claim 1, is characterized in that: described coupling agent be selected from vinyltriethoxysilane, γ-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane or atactic styrene-maleic anhydride copolymer one or more.
7. glass fiber reinforced polycarbonate matrix material according to claim 1, is characterized in that: described flow ability modifying agent be selected from fatty acid ester, cyclic butylene terephthalate, PE wax or ethylene bis-fatty acid amides one or more.
8. glass fiber reinforced polycarbonate matrix material according to claim 1, it is characterized in that: described oxidation inhibitor is selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) one or more in propionic acid positive octadecanol ester, three [2.4-di-tert-butyl-phenyl] phosphorous acid esters or two (2,4-DTBP) pentaerythritol diphosphites.
9. a preparation method for the arbitrary described glass fiber reinforced polycarbonate matrix material of claim 1 to 8, is characterized in that: comprise the following steps:
100 parts of PC resins, 3 ~ 20 parts of PETG resins, 1 ~ 8 part of toughner, 0.5 ~ 12 part of environmental protection fire retarding agent, 0.5 ~ 2 part of coupling agent, 1.0 ~ 4.0 parts of flow ability modifying agents and 0.3 ~ 1.0 part of oxidation inhibitor are mixed, the mixture of gained is added screw extrusion press extruding pelletization together with 15 ~ 50 parts of glass fibre, and tie rod pelletizing prepares glass fiber reinforced polycarbonate matrix material.
10. the preparation method of glass fiber reinforced polycarbonate matrix material according to claim 9, it is characterized in that: described in mix be carry out in high mixer, high mixer rotating speed is 500 ~ 700rpm, and mixing temperature is 60 ~ 90 DEG C, and mixing time is 3 ~ 8min;
Or described screw extrusion press is twin screw extruder, be 220 ~ 240 DEG C respectively, 230 ~ 250 DEG C, 250 ~ 270 DEG C, 260 ~ 275 DEG C, 260 ~ 270 DEG C, engine speed 20 ~ 50 hertz from spout to the extrusion temperature of extruder die head.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106118010A (en) * | 2016-08-24 | 2016-11-16 | 陈志凤 | A kind of PC alloy material and its preparation method and application |
| CN106349677A (en) * | 2016-09-22 | 2017-01-25 | 郑雯 | PC alloy material as well as preparation method and application thereof |
| CN106349673A (en) * | 2016-08-29 | 2017-01-25 | 王鹏 | PC alloy material and preparing method thereof |
| CN106543622A (en) * | 2016-10-20 | 2017-03-29 | 陈志凤 | Polyester is as flow improver additive in the purposes for improving enhancing ASA composition glossiness |
| CN106566218A (en) * | 2015-10-13 | 2017-04-19 | 上海杰事杰新材料(集团)股份有限公司 | Halogen-free, flame-retardant and antibacterial polycarbonate composite material and preparation method thereof |
| CN106905677A (en) * | 2015-12-22 | 2017-06-30 | 上海杰事杰新材料(集团)股份有限公司 | Halogen-free flameproof electromagnetic shielding makrolon material and preparation method thereof |
| CN107805378A (en) * | 2016-09-14 | 2018-03-16 | 谢湘 | A kind of PC alloy materials and its preparation method and application |
| CN107915978A (en) * | 2016-10-11 | 2018-04-17 | 成都金发科技新材料有限公司 | A kind of PC alloy materials and preparation method thereof |
| CN107915977A (en) * | 2016-10-09 | 2018-04-17 | 陈志凤 | A kind of PC alloy materials and preparation method thereof |
| CN108676341A (en) * | 2018-03-23 | 2018-10-19 | 佛山市南海承骏科技有限公司 | PC/PMMA/PETG ternary-alloy materials and preparation method thereof |
| CN109627771A (en) * | 2018-12-28 | 2019-04-16 | 南京时恒电子科技有限公司 | A kind of high intensity silicone material and its preparation method and application |
| CN109721995A (en) * | 2018-12-27 | 2019-05-07 | 会通新材料股份有限公司 | A kind of solvent resistant, polycarbonate composite material of high impact and preparation method thereof |
| CN110128809A (en) * | 2019-06-04 | 2019-08-16 | 昆山顺威工程塑料有限公司 | A kind of high-performance anti-floating fibre high glaze enhancing fire retardation PC material and preparation method thereof |
| WO2019231984A1 (en) * | 2018-05-31 | 2019-12-05 | Polyone Corporation | Flame retardant continuous fiber reinforced thermoplastic tape |
| CN112480637A (en) * | 2020-12-08 | 2021-03-12 | 上海通原环保科技有限公司 | Floating fiber-free flame-retardant PC/ABS composite material |
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| CN106566218A (en) * | 2015-10-13 | 2017-04-19 | 上海杰事杰新材料(集团)股份有限公司 | Halogen-free, flame-retardant and antibacterial polycarbonate composite material and preparation method thereof |
| CN106905677A (en) * | 2015-12-22 | 2017-06-30 | 上海杰事杰新材料(集团)股份有限公司 | Halogen-free flameproof electromagnetic shielding makrolon material and preparation method thereof |
| CN106118010A (en) * | 2016-08-24 | 2016-11-16 | 陈志凤 | A kind of PC alloy material and its preparation method and application |
| CN106349673A (en) * | 2016-08-29 | 2017-01-25 | 王鹏 | PC alloy material and preparing method thereof |
| CN107805378A (en) * | 2016-09-14 | 2018-03-16 | 谢湘 | A kind of PC alloy materials and its preparation method and application |
| CN106349677A (en) * | 2016-09-22 | 2017-01-25 | 郑雯 | PC alloy material as well as preparation method and application thereof |
| CN106349677B (en) * | 2016-09-22 | 2018-10-02 | 郑雯 | A kind of PC alloy materials and its preparation method and application |
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