CN103693985A - Preparation method of gradient carbon fiber/hydroxyapatite (HA) composite material - Google Patents
Preparation method of gradient carbon fiber/hydroxyapatite (HA) composite material Download PDFInfo
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Abstract
The invention relates to a preparation method of a gradient carbon fiber/hydroxyapatite (HA) composite material. The method comprises the following steps: performing compound modification on carbon fibers via low-temperature oxidation and a HA membrane layer pulling and drawing method; dispersing nanometer HA powder, an organic monomer acrylamide, a cross-linking agent N, N-methylene bisacrylamide, a dispersant sodium hexametaphosphate, an initiator ammonium persulfate, a catalyst N,N,N',N'-tetramethylethylenediamine and ammonium hydroxide into deionized water so as to prepare modified carbon fiber-HA duplex ceramic slurry; performing centrifugal molding on the duplex ceramic slurry; then taking out a centrifugal barrel and putting the centrifugal barrel into a water bath kettle so as to realize the curing molding of modified carbon fiber-HA gel; demolding a green body and then drying the green body in a drying box; and sintering the green body under the argon atmosphere in a tubular furnace so as to obtain the gradient carbon fiber-HA composite material. The method has the advantages that the content of carbon fibers at the bottom of the composite material is high, so that the strength and the toughness of the composite material can be improved during the load bearing; the content of HA at the top of the composite material is high, so that the osteoinduction and the biocompatibility of the composite material can be improved when the composite material is implanted into a human body; the centrifugal molding technology is adopted, so that the problem of stress concentration caused by the reason that the carbon fibers are likely to agglomerate during the dry pressing is solved, and thus the mechanical property of the composite material is improved.
Description
Technical field
The present invention is a kind of preparation method of gradient carbon fiber/hydroxyapatite composite material.
Background technology
Hydroxyapatite is called for short HA, its osteoconductive, biocompatibility, interfacial activity are all better than all kinds of conventional medical titanium alloys, silicon rubber and bone grafting carbon materials, can be for making transplanting in filling material of bone, artificial dental root, artificial jawbone, artificial nose's cartilage, skin, Middle Ear Implant ventpipe material etc., it is a kind of very promising bio-medical material, but HA material enbrittles, height, folding strength are low, the shortcomings such as self poor mechanical property, limit its range of application.Carbon fiber (CF) is the ceramic of a class mechanical property excellence, without creep, and antifatigue, thermal expansivity is little, and Young's modulus is high, nontoxic, good biocompatibility, is a kind of ideal strongthener, has been widely used in the fields such as medical science, life science.But because thermal expansivity and the surface chemical property difference of HA and carbon fiber are larger, make the interface bond strength of carbon fiber/HA matrix material poor, and there are a large amount of crackles, cause carbon fiber/HA composite materials property poor, limit it in the application in bio-medical field.Therefore the interface combination that how to improve both is a key issue.The preparation of traditional carbon fibres/HA matrix material simultaneously adopts dry pressuring forming process more.The dry-pressing formed reunion of carbon fiber can not avoid carbon fiber and HA powder batch mixing time, and carbon fiber and HA intergranular stress are concentrated during compression moulding.The reunion of this carbon fiber and stress concentration can cause distortion and the cracking of composite sample in sintering process, reduce the mechanical property of matrix material.In addition,, when carbon fiber content is more, although improved the mechanical property of matrix material, now the content of HA matrix reduces, and has reduced good osteoinductive and the affinity of HA material, has affected the biocompatibility of embedded material and body bone tissue.
Summary of the invention
The object of the invention is to, solve above-mentioned existing problem, the preparation method who improves the mechanical property of matrix material and a kind of gradient carbon fiber/hydroxyapatite composite material of osteoinductive and biocompatibility is provided.
Technical scheme of the present invention is: first carbon fiber is undertaken composite modified by low-temperature oxidation and the method that lifts HA rete, then by nanometer HA powder, organic monomer acrylamide (AM), linking agent N,N methylene bis acrylamide (MBAM), sodium hexametaphosphate dispersant ((NaPO
3)
6), initiator ammonium persulfate ((NH
4)
2s
2o
8), catalyst n, N, N ', N '-Tetramethyl Ethylene Diamine (TEMED) and ammoniacal liquor (NH
3h
2o) be distributed in deionized water and prepare modified carbon fiber-HA complex phase ceramic slurry, then by complex phase ceramic slurry centrifugal forming under different revolutions, then centrifugal barrel is taken out and to put into water-bath and make the moulding of modified carbon fiber-HA gel solidification.After the green compact demoulding, after loft drier inner drying 24h, in tube furnace, argon gas atmosphere sinters gradient carbon fiber-HA matrix material into.
Be specially:
1, carbon fiber is composite modified
A. carbon fiber is placed in to crucible and puts into and be warming up to the chamber type electric resistance furnace of 300-500 ℃ and be incubated 30min, standby through the pretreated carbon fiber of low-temperature oxidation;
B. compound concentration is the Ca (NO of 2 mol/L
3)
2alcoholic solution 100 mL, concentration is the P of 4 mol/L
2o
5alcoholic solution 117 mL, guarantee that Ca/P ratio is 1.67, by P
2o
5alcoholic solution is to Ca (NO
3)
2alcoholic solution 1-2mL/min drips, and magnetic agitation 2 h, after reaction finishes, becomes transparent thick colloidal sol, is HA colloidal sol;
C. pretreated carbon fiber before being put into the HA colloidal sol preparing soaks 5 minutes, then take out baking oven inner drying 1 h that puts into 80 ℃, make HA colloidal sol be transformed into HA gel, repeat this process 5 times, make to form one deck good HA coating of matrix combination with it at carbon fiber surface.It is that the staple fibre of 1mm is standby that carbon fiber after modification is cut into length.
2, the preparation of modified carbon fiber-HA complex phase ceramic slurry
A. press mass fraction, get the HA powder that 40-55 part granularity is 60nm, carbon fiber after the modification of 0.2-1.375 part, the acrylamide of 10 parts, the N,N methylene bis acrylamide of 0.5 part, the Sodium hexametaphosphate 99 of 2-2.75 part, 0.1 part of ammonium persulphate, 0.05-0.125 part N, N, N ', N '-Tetramethyl Ethylene Diamine, 30.15-47.15 part deionized water is standby;
B. get the deionized water of 30.15-47.15 part, the acrylamide of 10 parts, the N of 0.5 part, the Sodium hexametaphosphate 99 of N-methylene-bisacrylamide, 2-2.75 part is put into container, after stirring, drip the ammoniacal liquor that concentration is 10 mol/L, the pH that adjusts solution is 9-11, add 40-55 part HA powder to stir, after ball milling 24 h, add carbon fiber after the modification of 0.2-1.375 part, then after ball milling 24 h, obtain modified carbon fiber-HA complex phase ceramic slurry.
3, centrifugal forming and sintering
A. the above-mentioned modified carbon fiber-HA complex phase slurry preparing is injected in centrifugal barrel, centrifugal 5-20 min under 500-2000 r/min rotating speed, make modified carbon fiber and HA particle in centrifugal barrel, form Gradient distribution, then centrifugal barrel is taken out and put into 60 ℃ of insulation 10 min of water-bath, make the moulding of modified carbon fiber-HA gel solidification;
B. by the green compact demoulding from centrifugal barrel after solidifying, green compact are placed in loft drier after 70 ℃ of dry 24 h, put into and under tube furnace argon gas atmosphere, sinter gradient carbon fiber/HA matrix material into.Its sintering process is: adopt the temperature rise rate of 3 ℃/min to be heated to 400 ℃ from room temperature, after insulation 3 h, with the temperature rise rate of 5 ℃/min, be heated to 1100-1200 ℃, after insulation 2-4 h, with stove, be as cold as room temperature, wherein the flow velocity of argon gas is 0.2-0.5 L/min.
The invention has the advantages that:
1. the structure of gradient carbon fiber/HA matrix material, see Fig. 1, wherein bottom carbon fiber content is higher, contributes to improve intensity and the toughness of matrix material when bearing load, top HA content is higher, contributes to improve osteoinductive and the biocompatibility of matrix material when implant into body; Even carbon fiber/HA matrix material that compressive strength, fracture toughness are all made higher than traditional dry pressuring forming process, in Table 1.
2. centrifugal forming combines the advantage of the preparation of wet method powder and unstressed densification technology, is a kind of near net shape technology that is applicable to complicated shape, large-size components.The reunion of carbon fiber when centrifugal forming can be avoided carbon fiber and HA powder batch mixing, make carbon fiber dispersed in HA slurry inside, while avoiding dry-pressing, carbon fiber and HA intergranular stress are concentrated simultaneously, fine and close unstressed the concentrating of centrifugal rear green compact, can be at lower temperature densified sintering product, reduce distortion and the cracking of sintered product, the problem of avoiding HA high temperature sintering to decompose.
The compression performance of the even carbon fiber/HA matrix material of table 1 and gradient carbon fiber/HA matrix material
| Sample | Compressive strength (MPa) | Fracture toughness MPa.m 1/2 |
| Even carbon fiber/HA matrix material | 73.2 | 1.76 |
| Gradient carbon fiber/HA matrix material | 99.6 | 1.98 |
Note: evenly carbon fiber/HA matrix material is traditional dry pressuring forming process preparation, gradient carbon fiber/HA matrix material is centrifugal molding process preparation of the present invention.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention will be further described:
Example 1
1, carbon fiber is composite modified
A. carbon fiber is placed in to crucible and puts into and be warming up to the chamber type electric resistance furnace of 300 ℃ and be incubated 30min, standby through the pretreated carbon fiber of low-temperature oxidation;
B. compound concentration is the Ca (NO of 2 mol/L
3)
2alcoholic solution 100 mL, concentration is the P of 4 mol/L
2o
5alcoholic solution 117 mL, guarantee that Ca/P ratio is 1.67, by P
2o
5alcoholic solution is to Ca (NO
3)
2alcoholic solution 1mL/min drips, and magnetic agitation 2 h, after reaction finishes, becomes transparent thick colloidal sol;
C. pretreated carbon fiber before being put into the HA colloidal sol preparing soaks 5 minutes, then take out baking oven inner drying 1 h that puts into 80 ℃, make HA colloidal sol be transformed into HA gel, repeat this process 5 times, make to form one deck good HA coating of matrix combination with it at carbon fiber surface.It is that the staple fibre of 1mm is standby that carbon fiber after modification is cut into length.
2, the preparation of modified carbon fiber-HA complex phase ceramic slurry
A. press mass fraction, get the HA powder that 40 parts of granularities are 60nm, carbon fiber after 0.2 part of modification, the acrylamide of 10 parts, the N,N methylene bis acrylamide of 0.5 part, the Sodium hexametaphosphate 99 of 2 parts, 0.1 part of ammonium persulphate, 0.05 part of N, N, N ', N '-Tetramethyl Ethylene Diamine, 47.15 parts of deionized waters are standby;
B.47.15 in part deionized water, add the acrylamide of 10 parts, the N of 0.5 part, N-methylene-bisacrylamide, the Sodium hexametaphosphate 99 of 2 parts, after stirring, drip the ammoniacal liquor that concentration is 10 mol/L, the pH that adjusts solution is 9, add 40 parts of HA powder to stir, after ball milling 24 h, add carbon fiber after 0.2 part of modification, then after ball milling 24 h, obtain modified carbon fiber-HA complex phase ceramic slurry.
3, centrifugal forming and sintering
A. the above-mentioned modified carbon fiber-HA complex phase slurry preparing is injected in centrifugal barrel, centrifugal 20 min under 500 r/min rotating speeds, make modified carbon fiber and HA particle in centrifugal barrel, form Gradient distribution, then centrifugal barrel is taken out and put into 60 ℃ of insulation 10 min of water-bath, make the moulding of modified carbon fiber-HA gel solidification;
B. by the green compact demoulding from centrifugal barrel after solidifying, green compact are placed in loft drier after 70 ℃ of dry 24 h, put into and under tube furnace argon gas atmosphere, sinter gradient carbon fiber/HA matrix material into.Its sintering process is: adopt the temperature rise rate of 3 ℃/min to be heated to 400 ℃ from room temperature, after insulation 3 h, with the temperature rise rate of 5 ℃/min, be heated to 1200 ℃, after insulation 2 h, with stove, be as cold as room temperature, wherein the flow velocity of argon gas is 0.5 L/min.
Example 2
1, carbon fiber is composite modified
A. carbon fiber is placed in to crucible and puts into and be warming up to the chamber type electric resistance furnace of 500 ℃ and be incubated 30min, standby through the pretreated carbon fiber of low-temperature oxidation;
B. compound concentration is the Ca (NO of 2 mol/L
3)
2alcoholic solution 100 mL, concentration is the P of 4 mol/L
2o
5alcoholic solution 117 mL, guarantee that Ca/P ratio is 1.67, by P
2o
5alcoholic solution is to Ca (NO
3)
2alcoholic solution 1mL/min drips, and magnetic agitation 2 h, after reaction finishes, becomes transparent thick colloidal sol;
C. pretreated carbon fiber before being put into the HA colloidal sol preparing soaks 5 minutes, then take out baking oven inner drying 1 h that puts into 80 ℃, make HA colloidal sol be transformed into HA gel, repeat this process 5 times, make to form one deck good HA coating of matrix combination with it at carbon fiber surface.It is that the staple fibre of 1mm is standby that carbon fiber after modification is cut into length.
2, the preparation of modified carbon fiber-HA complex phase ceramic slurry
A. press mass fraction, get the HA powder that 55 parts of granularities are 60nm, carbon fiber after 1.375 parts of modifications, the acrylamide of 10 parts, the N,N methylene bis acrylamide of 0.5 part, the Sodium hexametaphosphate 99 of 2.75 parts, 0.1 part of ammonium persulphate, 0.125 part of N, N, N ', N '-Tetramethyl Ethylene Diamine, 30.15 parts of deionized waters are standby;
B.30.15 in part deionized water, add the acrylamide of 10 parts, the N of 0.5 part, N-methylene-bisacrylamide, the Sodium hexametaphosphate 99 of 2.75 parts, after stirring, drip the ammoniacal liquor that concentration is 10 mol/L, the pH that adjusts solution is 11, add 55 parts of HA powder to stir, after ball milling 24 h, add carbon fiber after 1.375 parts of modifications, then after ball milling 24 h, obtain modified carbon fiber-HA complex phase ceramic slurry.
3, centrifugal forming and sintering
A. the above-mentioned modified carbon fiber-HA complex phase slurry preparing is injected in centrifugal barrel, centrifugal 5 min under 2000 r/min rotating speeds, make modified carbon fiber and HA particle in centrifugal barrel, form Gradient distribution, then centrifugal barrel is taken out and put into 60 ℃ of insulation 10 min of water-bath, make the moulding of modified carbon fiber-HA gel solidification;
B. by the green compact demoulding from centrifugal barrel after solidifying, green compact are placed in loft drier after 70 ℃ of dry 24 h, put into and under tube furnace argon gas atmosphere, sinter gradient carbon fiber/HA matrix material into.Its sintering process is: adopt the temperature rise rate of 3 ℃/min to be heated to 400 ℃ from room temperature, after insulation 3 h, with the temperature rise rate of 5 ℃/min, be heated to 1100 ℃, after insulation 4 h, with stove, be as cold as room temperature, wherein the flow velocity of argon gas is 0.2 L/min.
Example 3
1, carbon fiber is composite modified
A. carbon fiber is placed in to crucible and puts into and be warming up to the chamber type electric resistance furnace of 400 ℃ and be incubated 30 min, standby through the pretreated carbon fiber of low-temperature oxidation;
B. compound concentration is the Ca (NO of 2 mol/L
3)
2alcoholic solution 100 mL, concentration is the P of 4 mol/L
2o
5alcoholic solution 117 mL, guarantee that Ca/P ratio is 1.67, by P
2o
5alcoholic solution is to Ca (NO
3)
2alcoholic solution 1.5mL/min drips, and magnetic agitation 2 h, after reaction finishes, becomes transparent thick colloidal sol;
C. pretreated carbon fiber before being put into the HA colloidal sol preparing soaks 5 minutes, then take out baking oven inner drying 1 h that puts into 80 ℃, make HA colloidal sol be transformed into HA gel, repeat this process 5 times, make to form one deck good HA coating of matrix combination with it at carbon fiber surface.It is that the staple fibre of 1mm is standby that carbon fiber after modification is cut into length.
2, the preparation of modified carbon fiber-HA complex phase ceramic slurry
A. press mass fraction, get the HA powder that 50 parts of granularities are 60 nm, carbon fiber after 1 part of modification, the acrylamide of 10 parts, the N,N methylene bis acrylamide of 0.5 part, the Sodium hexametaphosphate 99 of 2.5 parts, 0.1 part of ammonium persulphate, 0.1 part of N, N, N ', N '-Tetramethyl Ethylene Diamine, 35.8 parts of deionized waters are standby;
B.50 in part deionized water, add the acrylamide of 10 parts, the N of 0.5 part, N-methylene-bisacrylamide, the Sodium hexametaphosphate 99 of 2.5 parts, after stirring, drip the ammoniacal liquor that concentration is 10 mol/L, the pH that adjusts solution is 10, add 50 parts of HA powder to stir, after ball milling 24 h, add carbon fiber after 1 part of modification, then after ball milling 24 h, obtain modified carbon fiber-HA complex phase ceramic slurry.
3, centrifugal forming and sintering
A. the above-mentioned modified carbon fiber-HA complex phase slurry preparing is injected in centrifugal barrel, centrifugal 10 min under 1500 r/min rotating speeds, make modified carbon fiber and HA particle in centrifugal barrel, form Gradient distribution, then centrifugal barrel is taken out and put into 60 ℃ of insulation 10 min of water-bath, make the moulding of modified carbon fiber-HA gel solidification;
B. by the green compact demoulding from centrifugal barrel after solidifying, green compact are placed in loft drier after 70 ℃ of dry 24 h, put into and under tube furnace argon gas atmosphere, sinter gradient carbon fiber/HA matrix material into.Its sintering process is: adopt the temperature rise rate of 3 ℃/min to be heated to 400 ℃ from room temperature, after insulation 3 h, with the temperature rise rate of 5 ℃/min, be heated to 1150 ℃, after insulation 3 h, with stove, be as cold as room temperature, wherein the flow velocity of argon gas is 0.4 L/min.
Example 4
1, carbon fiber is composite modified
A. carbon fiber is placed in to crucible and puts into and be warming up to the chamber type electric resistance furnace of 350 ℃ and be incubated 30 min, standby through the pretreated carbon fiber of low-temperature oxidation;
B. compound concentration is the Ca (NO of 2 mol/L
3)
2alcoholic solution 100 mL, concentration is the P of 4 mol/L
2o
5alcoholic solution 117 mL, guarantee that Ca/P ratio is 1.67, by P
2o
5alcoholic solution is to Ca (NO
3)
2alcoholic solution 2mL/min drips, and magnetic agitation 2 h, becomes transparent thick colloidal sol, i.e. HA colloidal sol after reaction finishes;
C. pretreated carbon fiber before being put into the HA colloidal sol preparing soaks 5 minutes, then take out baking oven inner drying 1 h that puts into 80 ℃, make HA colloidal sol be transformed into HA gel, repeat this process 5 times, make to form one deck good HA coating of matrix combination with it at carbon fiber surface.It is that the staple fibre of 1mm is standby that carbon fiber after modification is cut into length.
2, the preparation of modified carbon fiber-HA complex phase ceramic slurry
A. press mass fraction, get the HA powder that 45 parts of granularities are 60nm, carbon fiber after 0.45 part of modification, the acrylamide of 10 parts, the N,N methylene bis acrylamide of 0.5 part, the Sodium hexametaphosphate 99 of 2.25 parts, 0.1 part of ammonium persulphate, 0.075 part of N, N, N ', N '-Tetramethyl Ethylene Diamine, 41.625 parts of deionized waters are standby;
B.41.625 in part deionized water, add the acrylamide of 10 parts, the N of 0.5 part, N-methylene-bisacrylamide, the Sodium hexametaphosphate 99 of 2.25 parts, after stirring, drip the ammoniacal liquor that concentration is 10 mol/L, the pH that adjusts solution is 10, add 45 parts of HA powder to stir, after ball milling 24 h, add carbon fiber after 0.45 part of modification, then after ball milling 24 h, obtain modified carbon fiber-HA complex phase ceramic slurry.
3, centrifugal forming and sintering
A. the above-mentioned modified carbon fiber-HA complex phase slurry preparing is injected in centrifugal barrel, centrifugal 15 min under 1000 r/min rotating speeds, make modified carbon fiber and HA particle in centrifugal barrel, form Gradient distribution, then centrifugal barrel is taken out and put into 60 ℃ of insulation 10 min of water-bath, make the moulding of modified carbon fiber-HA gel solidification;
B. by the green compact demoulding from centrifugal barrel after solidifying, green compact are placed in loft drier after 70 ℃ of dry 24 h, put into and under tube furnace argon gas atmosphere, sinter gradient carbon fiber/HA matrix material into.Its sintering process is: adopt the temperature rise rate of 3 ℃/min to be heated to 400 ℃ from room temperature, after insulation 3 h, with the temperature rise rate of 5 ℃/min, be heated to 1500 ℃, after insulation 3 h, with stove, be as cold as room temperature, wherein the flow velocity of argon gas is 0.3 L/min.
Above-mentioned carbon fiber used is that Dalian Xingke Carbon Fiber Co., Ltd produces; Hydroxyapatite powder is that Nanjing Ai Pu nano material company limited produces.
Claims (5)
1. a preparation method for gradient carbon fiber/hydroxyapatite composite material, is characterized in that,
One, carbon fiber is composite modified
A. carbon fiber is placed in to crucible and puts into and be warming up to the chamber type electric resistance furnace of 300-500 ℃ and be incubated 30min, standby through the pretreated carbon fiber of low-temperature oxidation;
B. compound concentration is the Ca (NO of 2 mol/L
3)
2alcoholic solution 100 mL, concentration is the P of 4 mol/L
2o
5alcoholic solution 117 mL, guarantee that Ca/P ratio is 1.67, by P
2o
5alcoholic solution is to Ca (NO
3)
2alcoholic solution 1-2mL/min drips,, and magnetic agitation 2 h, after finishing, reaction becomes transparent thick colloidal sol, be HA colloidal sol;
C. pretreated carbon fiber before being put into the HA colloidal sol preparing soaks 5 minutes, then take out baking oven inner drying 1 h that puts into 80 ℃, make HA colloidal sol be transformed into HA gel, repeat this process 5 times, make to form one deck good HA coating of matrix combination with it at carbon fiber surface; It is that the staple fibre of 1mm is standby that carbon fiber after modification is cut into length;
Two, the preparation of modified carbon fiber-HA complex phase ceramic slurry
A. press mass fraction, get the HA powder that 40-55 part granularity is 60nm, carbon fiber after the modification of 0.2-1.375 part, the acrylamide of 10 parts, the N,N methylene bis acrylamide of 0.5 part, the Sodium hexametaphosphate 99 of 2-2.75 part, 0.1 part of ammonium persulphate, 0.05-0.125 part N, N, N ', N '-Tetramethyl Ethylene Diamine, 30.15-47.15 part deionized water is standby;
B. get the deionized water of 30.15-47.15 part, the acrylamide of 10 parts, the N of 0.5 part, the Sodium hexametaphosphate 99 of N-methylene-bisacrylamide, 2-2.75 part is put into container, after stirring, drip the ammoniacal liquor that concentration is 10 mol/L, the pH that adjusts solution is 9-11, add 40-55 part HA powder to stir, after ball milling 24 h, add carbon fiber after the modification of 0.2-1.375 part, then after ball milling 24 h, obtain modified carbon fiber-HA complex phase ceramic slurry;
three, centrifugal forming and sintering
A. the above-mentioned modified carbon fiber-HA complex phase slurry preparing is injected in centrifugal barrel, centrifugal 5-20 min under 500-2000 r/min rotating speed, make modified carbon fiber and HA particle in centrifugal barrel, form Gradient distribution, then centrifugal barrel is taken out and put into 60 ℃ of insulation 10 min of water-bath, make the moulding of modified carbon fiber-HA gel solidification;
B. by the green compact demoulding from centrifugal barrel after solidifying, green compact are placed in loft drier after 70 ℃ of dry 24 h, put into and under tube furnace argon gas atmosphere, sinter gradient carbon fiber/HA matrix material into; Its sintering process is: adopt the temperature rise rate of 3 ℃/min to be heated to 400 ℃ from room temperature, after insulation 3 h, with the temperature rise rate of 5 ℃/min, be heated to 1100-1200 ℃, after insulation 2-4 h, with stove, be as cold as room temperature, wherein the flow velocity of argon gas is 0.2-0.5 L/min.
2. according to the preparation method of the said a kind of gradient carbon fiber/hydroxyapatite composite material of claim 1, it is characterized in that,
One, carbon fiber is composite modified
A. carbon fiber is placed in to crucible and puts into and be warming up to the chamber type electric resistance furnace of 300 ℃ and be incubated 30min, standby through the pretreated carbon fiber of low-temperature oxidation;
B. compound concentration is the Ca (NO of 2 mol/L
3)
2alcoholic solution 100 mL, concentration is the P of 4 mol/L
2o
5alcoholic solution 117 mL, guarantee that Ca/P ratio is 1.67, by P
2o
5alcoholic solution is to Ca (NO
3)
2alcoholic solution 1mL/min drips, and magnetic agitation 2 h, after reaction finishes, becomes transparent thick colloidal sol;
C. pretreated carbon fiber before being put into the HA colloidal sol preparing soaks 5 minutes, then take out baking oven inner drying 1 h that puts into 80 ℃, make HA colloidal sol be transformed into HA gel, repeat this process 5 times, make to form one deck good HA coating of matrix combination with it at carbon fiber surface; It is that the staple fibre of 1mm is standby that carbon fiber after modification is cut into length;
Two, the preparation of modified carbon fiber-HA complex phase ceramic slurry
A. press mass fraction, get the HA powder that 40 parts of granularities are 60nm, carbon fiber after 0.2 part of modification, the acrylamide of 10 parts, the N,N methylene bis acrylamide of 0.5 part, the Sodium hexametaphosphate 99 of 2 parts, 0.1 part of ammonium persulphate, 0.05 part of N, N, N ', N '-Tetramethyl Ethylene Diamine, 47.15 parts of deionized waters are standby;
B.47.15 in part deionized water, add the acrylamide of 10 parts, the N of 0.5 part, N-methylene-bisacrylamide, the Sodium hexametaphosphate 99 of 2 parts, after stirring, drip the ammoniacal liquor that concentration is 10 mol/L, the pH that adjusts solution is 9, add 40 parts of HA powder to stir, after ball milling 24 h, add carbon fiber after 0.2 part of modification, then after ball milling 24 h, obtain modified carbon fiber-HA complex phase ceramic slurry;
Three, centrifugal forming and sintering
A. the above-mentioned modified carbon fiber-HA complex phase slurry preparing is injected in centrifugal barrel, centrifugal 20 min under 500 r/min rotating speeds, make modified carbon fiber and HA particle in centrifugal barrel, form Gradient distribution, then centrifugal barrel is taken out and put into 60 ℃ of insulation 10 min of water-bath, make the moulding of modified carbon fiber-HA gel solidification;
B. by the green compact demoulding from centrifugal barrel after solidifying, green compact are placed in loft drier after 70 ℃ of dry 24 h, put into and under tube furnace argon gas atmosphere, sinter gradient carbon fiber/HA matrix material into; Its sintering process is: adopt the temperature rise rate of 3 ℃/min to be heated to 400 ℃ from room temperature, after insulation 3 h, with the temperature rise rate of 5 ℃/min, be heated to 1200 ℃, after insulation 2 h, with stove, be as cold as room temperature, wherein the flow velocity of argon gas is 0.5 L/min.
3. according to the preparation method of the said a kind of gradient carbon fiber/hydroxyapatite composite material of claim 1, it is characterized in that,
One, carbon fiber is composite modified
A. carbon fiber is placed in to crucible and puts into and be warming up to the chamber type electric resistance furnace of 500 ℃ and be incubated 30min, standby through the pretreated carbon fiber of low-temperature oxidation;
B. compound concentration is the Ca (NO of 2 mol/L
3)
2alcoholic solution 100 mL, concentration is the P of 4 mol/L
2o
5alcoholic solution 117 mL, guarantee that Ca/P ratio is 1.67, by P
2o
5alcoholic solution is to Ca (NO
3)
2alcoholic solution 1mL/min drips, and magnetic agitation 2 h, after reaction finishes, becomes transparent thick colloidal sol;
C. pretreated carbon fiber before being put into the HA colloidal sol preparing soaks 5 minutes, then take out baking oven inner drying 1 h that puts into 80 ℃, make HA colloidal sol be transformed into HA gel, repeat this process 5 times, make to form one deck good HA coating of matrix combination with it at carbon fiber surface; It is that the staple fibre of 1mm is standby that carbon fiber after modification is cut into length;
Two, the preparation of modified carbon fiber-HA complex phase ceramic slurry
A. press mass fraction, get the HA powder that 55 parts of granularities are 60nm, carbon fiber after 1.375 parts of modifications, the acrylamide of 10 parts, the N,N methylene bis acrylamide of 0.5 part, the Sodium hexametaphosphate 99 of 2.75 parts, 0.1 part of ammonium persulphate, 0.125 part of N, N, N ', N '-Tetramethyl Ethylene Diamine, 30.15 parts of deionized waters are standby;
B.30.15 in part deionized water, add the acrylamide of 10 parts, the N of 0.5 part, N-methylene-bisacrylamide, the Sodium hexametaphosphate 99 of 2.75 parts, after stirring, drip the ammoniacal liquor that concentration is 10 mol/L, the pH that adjusts solution is 11, add 55 parts of HA powder to stir, after ball milling 24 h, add carbon fiber after 1.375 parts of modifications, then after ball milling 24 h, obtain modified carbon fiber-HA complex phase ceramic slurry;
Three, centrifugal forming and sintering
A. the above-mentioned modified carbon fiber-HA complex phase slurry preparing is injected in centrifugal barrel, centrifugal 5 min under 2000 r/min rotating speeds, make modified carbon fiber and HA particle in centrifugal barrel, form Gradient distribution, then centrifugal barrel is taken out and put into 60 ℃ of insulation 10 min of water-bath, make the moulding of modified carbon fiber-HA gel solidification;
B. by the green compact demoulding from centrifugal barrel after solidifying, green compact are placed in loft drier after 70 ℃ of dry 24 h, put into and under tube furnace argon gas atmosphere, sinter gradient carbon fiber/HA matrix material into; Its sintering process is: adopt the temperature rise rate of 3 ℃/min to be heated to 400 ℃ from room temperature, after insulation 3 h, with the temperature rise rate of 5 ℃/min, be heated to 1100 ℃, after insulation 4 h, with stove, be as cold as room temperature, wherein the flow velocity of argon gas is 0.2 L/min.
4. according to the preparation method of the said a kind of gradient carbon fiber/hydroxyapatite composite material of claim 1, it is characterized in that,
One, carbon fiber is composite modified
A. carbon fiber is placed in to crucible and puts into and be warming up to the chamber type electric resistance furnace of 400 ℃ and be incubated 30 min, standby through the pretreated carbon fiber of low-temperature oxidation;
B. compound concentration is the Ca (NO of 2 mol/L
3)
2alcoholic solution 100 mL, concentration is the P of 4 mol/L
2o
5alcoholic solution 117 mL, guarantee that Ca/P ratio is 1.67, by P
2o
5alcoholic solution is to Ca (NO
3)
2alcoholic solution 1.5mL/min slowly drips, and magnetic agitation 2 h, after reaction finishes, becomes transparent thick colloidal sol;
C. pretreated carbon fiber before being put into the HA colloidal sol preparing soaks 5 minutes, then take out baking oven inner drying 1 h that puts into 80 ℃, make HA colloidal sol be transformed into HA gel, repeat this process 5 times, make to form one deck good HA coating of matrix combination with it at carbon fiber surface; It is that the staple fibre of 1mm is standby that carbon fiber after modification is cut into length;
Two, the preparation of modified carbon fiber-HA complex phase ceramic slurry
A. press mass fraction, get the HA powder that 50 parts of granularities are 60 nm, carbon fiber after 1 part of modification, the acrylamide of 10 parts, the N,N methylene bis acrylamide of 0.5 part, the Sodium hexametaphosphate 99 of 2.5 parts, 0.1 part of ammonium persulphate, 0.1 part of N, N, N ', N '-Tetramethyl Ethylene Diamine, 35.8 parts of deionized waters are standby;
B.50 in part deionized water, add the acrylamide of 10 parts, the N of 0.5 part, N-methylene-bisacrylamide, the Sodium hexametaphosphate 99 of 2.5 parts, after stirring, drip the ammoniacal liquor that concentration is 10 mol/L, the pH that adjusts solution is 10, add 50 parts of HA powder to stir, after ball milling 24 h, add carbon fiber after 1 part of modification, then after ball milling 24 h, obtain modified carbon fiber-HA complex phase ceramic slurry;
Three, centrifugal forming and sintering
A. the above-mentioned modified carbon fiber-HA complex phase slurry preparing is injected in centrifugal barrel, centrifugal 10 min under 1500 r/min rotating speeds, make modified carbon fiber and HA particle in centrifugal barrel, form Gradient distribution, then centrifugal barrel is taken out and put into 60 ℃ of insulation 10 min of water-bath, make the moulding of modified carbon fiber-HA gel solidification;
B. by the green compact demoulding from centrifugal barrel after solidifying, green compact are placed in loft drier after 70 ℃ of dry 24 h, put into and under tube furnace argon gas atmosphere, sinter gradient carbon fiber/HA matrix material into; Its sintering process is: adopt the temperature rise rate of 3 ℃/min to be heated to 400 ℃ from room temperature, after insulation 3 h, with the temperature rise rate of 5 ℃/min, be heated to 1150 ℃, after insulation 3 h, with stove, be as cold as room temperature, wherein the flow velocity of argon gas is 0.4 L/min.
5. according to the preparation method of the said a kind of gradient carbon fiber/hydroxyapatite composite material of claim 1, it is characterized in that,
One, carbon fiber is composite modified
A. carbon fiber is placed in to crucible and puts into and be warming up to the chamber type electric resistance furnace of 350 ℃ and be incubated 30 min, standby through the pretreated carbon fiber of low-temperature oxidation;
B. compound concentration is the Ca (NO of 2 mol/L
3)
2alcoholic solution 100 mL, concentration is the P of 4 mol/L
2o
5alcoholic solution 117 mL, guarantee that Ca/P ratio is 1.67, by P
2o
5alcoholic solution is to Ca (NO
3)
2alcoholic solution 2mL/min slowly drips, and magnetic agitation 2 h, becomes transparent thick colloidal sol, i.e. HA colloidal sol after reaction finishes;
C. pretreated carbon fiber before being put into the HA colloidal sol preparing soaks 5 minutes, then take out baking oven inner drying 1 h that puts into 80 ℃, make HA colloidal sol be transformed into HA gel, repeat this process 5 times, make to form one deck good HA coating of matrix combination with it at carbon fiber surface; It is that the staple fibre of 1mm is standby that carbon fiber after modification is cut into length;
Two, the preparation of modified carbon fiber-HA complex phase ceramic slurry
A. press mass fraction, get the HA powder that 45 parts of granularities are 60nm, carbon fiber after 0.45 part of modification, the acrylamide of 10 parts, the N,N methylene bis acrylamide of 0.5 part, the Sodium hexametaphosphate 99 of 2.25 parts, 0.1 part of ammonium persulphate, 0.075 part of N, N, N ', N '-Tetramethyl Ethylene Diamine, 41.625 parts of deionized waters are standby;
B.41.625 in part deionized water, add the acrylamide of 10 parts, the N of 0.5 part, N-methylene-bisacrylamide, the Sodium hexametaphosphate 99 of 2.25 parts, after stirring, drip the ammoniacal liquor that concentration is 10 mol/L, the pH that adjusts solution is 10, add 45 parts of HA powder to stir, after ball milling 24 h, add carbon fiber after 0.45 part of modification, then after ball milling 24 h, obtain modified carbon fiber-HA complex phase ceramic slurry;
Three, centrifugal forming and sintering
A. the above-mentioned modified carbon fiber-HA complex phase slurry preparing is injected in centrifugal barrel, centrifugal 15 min under 1000 r/min rotating speeds, make modified carbon fiber and HA particle in centrifugal barrel, form Gradient distribution, then centrifugal barrel is taken out and put into 60 ℃ of insulation 10 min of water-bath, make the moulding of modified carbon fiber-HA gel solidification;
B. by the green compact demoulding from centrifugal barrel after solidifying, green compact are placed in loft drier after 70 ℃ of dry 24 h, put into and under tube furnace argon gas atmosphere, sinter gradient carbon fiber/HA matrix material into; Its sintering process is: adopt the temperature rise rate of 3 ℃/min to be heated to 400 ℃ from room temperature, after insulation 3 h, with the temperature rise rate of 5 ℃/min, be heated to 1500 ℃, after insulation 3 h, with stove, be as cold as room temperature, wherein the flow velocity of argon gas is 0.3 L/min.
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| CN104129926A (en) * | 2014-08-08 | 2014-11-05 | 太仓派欧技术咨询服务有限公司 | Glass fiber with biocompatible hydroxyapatite on surface |
| CN104193378A (en) * | 2014-08-21 | 2014-12-10 | 海安县中山合成纤维有限公司 | Modified-carbon-fiber-reinforced HA (hyaluronic acid) composite material |
| CN110079799A (en) * | 2019-06-18 | 2019-08-02 | 徐州徐工基础工程机械有限公司 | A kind of preparation method of the surface graded wear-resistant coating of shaft-like workpiece |
| CN110723972A (en) * | 2019-10-16 | 2020-01-24 | 安徽工程大学 | CNTs toughening ZrB2Preparation method of ultrahigh-temperature ceramic composite material |
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| WO2006115755A2 (en) * | 2005-04-27 | 2006-11-02 | Ucar Carbon Company Inc. | Manufacturing carbon fiber reinforced ceramics as brake discs |
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