CN101603160B - Hydroxyapatite whisker and magnesium metal base composite material and preparation method thereof - Google Patents
Hydroxyapatite whisker and magnesium metal base composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a hydroxyapatite whisker and magnesium metal base composite material and a preparation method thereof. The composite material consists of magnesium metal as a base material and hydroxyapatite as a reinforcement, wherein the magnesium metal is of pure magnesium powder, the hydroxyapatite has a whisker shape, the hydroxyapatite accounts for 1 to 30 percent by weight, and the magnesium powder accounts for 70 to 99 percent by weight. The preparation method of the composite material comprises the following steps: (1) thinning treatment of the magnesium powder; (2) preparation of the hydroxyapatite whisker; (3) mixing of the hydroxyapatite whisker and the magnesium powder; (4) pressing and sintering; and (5) thermal extrusion. The reinforcement whisker has the advantages of even distribution, low damaged degree and size controllability, ensures the bioactivity of the composite material, and also can improve the corrosion rate and mechanical property of the composite material. The preparation method is simple and has little pollution in the process; and the hydroxyapatite whisker and magnesium metal base composite material is particularly suitable for repairing and replacing bone tissues.
Description
Technical field
The invention relates to Biodegradable hydroxylapatite whisker/magnesium metal base composite material and preparation method thereof, belong to biomedical materials field.
Background technology
Magnesium and alloy thereof are a kind of ideal hard tissue implanting materials, and its density has only 1.74g/cm
3Fracture toughness is than bioceramic, and as the hydroxyapatite height, and elastic modelling quantity and compressive strength with the active service biomedical metal material, are compared as rustless steel, titanium alloy, more near natural bone.The most important thing is that magnesium is degradable in the human body environment, the catabolite of formation is nontoxic solvable, can get rid of with urine, to not infringement of health.Studies show that magnesium ion plays an important role to the human body metabolism.The normal adult of one individual weight 70kg has the 1mol magnesium ion approximately in the body, wherein make an appointment with half to be stored in the osseous tissue.Magnesium makes to it is believed that magnesium may stimulate new bone growth to the effect of function of human body and the existence in bone.So the magnesium metal material is expected to become the shaping reparation embedded material of degradable and loadable lotus.But studies show that at present the corrosion in human body environment (the about 7.4-7.6 of pH, high chlorine) of available magnesium alloy is too fast, produce excessive hydrogen and high pH value easily in the part, thereby influence the biocompatibility and the mechanical property of material.As seen, the degradation speed of control magnesium alloy is a primary goal of improving the magnesium alloy performance, and its method mainly contains machining, alloying and surface modification.
But replace and repair and use metal material as the osseous tissue of load-bearing, should have excellent biological compatibility, mechanical properties such as regulatable degradation rate and proper intensity, toughness, elastic modelling quantity, wearability.From existing report, machining, alloying and surface modification can only be improved a certain of magnesium and alloy thereof or two kinds of performances, the not obvious or deterioration to other performance improvements.And, add hydroxyapatite and strengthen intensity and the biological activity that body both can improve matrix, and, also reduced the degradation rate of composite integral body because hydroxyapatite solubility in the human body environment is low by even compound mode.It is less that relevant hydroxyapatite strengthens the magnesium metal composite study.German scholar (Biodegradable magnesium/hydroxyapaptite metal matrix composites, Biomaterials, 2007 (28); Chinese patent, publication number CN 101330933A) prepared hydroxyapatite enhancing AZ91 composite material of magnesium alloy with powder metallurgic method.The hydroxyapatite size is less than 44 μ m, and pattern is not described.The result shows that this material has excellent biological compatibility; In artificial sea water and cell culture fluid, the adding of hydroxyapatite can both form protective layer at composite material surface, thereby improves the resistance to corrosion of magnesium alloy substrate.But hydroxyapatite is skewness in matrix, add mechanical ball milling after, the apatite of hard crisp phase is irregular, it is serious to reunite, not obvious to the contribution of mechanical property.(Chinese patent, publication number CN101185777A) such as Chinese scholar Chen Min virtues invented a kind of degradable nano hydroxyapatite lime stone/magnesium alloy blood vessel inner bracket material.The alloy element of base material magnesium alloy is zinc and zirconium.The addition of hydroxyapatite is 0.1wt%～5wt%, diameter 10～15nm, and long 100～200nm is nano bar-shape.But do not describe distribution, reunion situation and the pattern of the compound back of material hydroxyapatite in the literary composition, only mention in experiment content, material needs powerful the stirring a period of time in recombination process.According to our experiment experience, the size that strengthens body material enhancing body under brute force stirs can be had a strong impact on, and length generally can drop to below the 50nm.Chinese scholar Liu De treasured (preparation of HA/Mg Biocomposite material and etching characteristic thereof, Rare Metals Materials and engineering, 2008,37 (12)) be matrix with pure magnesium, needle-like hydroxyapatite (HA) powder body with the chemical precipitation method preparation serves as to strengthen body, adopts powder metallurgical technique to prepare the HA/Mg composite of different hydroxyapatite content.The addition of hydroxyapatite is 20～40vol%, is needle-like, and length is 400～1000nm.The result shows that significant reaction does not take place for HA and magnesium matrix in the sintering process; The adding of HA can improve the resistance to corrosion of composite in simulated body fluid; Along with the increase of HA content, the hardness of composite increases, and relative density and tensile strength descend.Do not explain the pattern and the distribution of compound back hydroxyapatite in the literary composition, only mentioning the enhancing body has local agglomeration.
From the preliminary study result of hydroxyapatite/magnesium metal base composite material as can be seen, there is following problem in the hydroxyapatite/magnesium metal base composite material of existing preparation: (1) hydroxyapatite strengthens body and is mainly elongated piece, length is lower than 1000nm, easy fracture in powerful whipping process, be irregular, reduced the contribution of hydroxyapatite composite materials property; (2) hydroxyapatite strengthens body and disperses inhomogeneously in the dry blending process, easily is aggregating state, is unfavorable for the sintering densification of composite.
Summary of the invention
At the prior art above shortcomings, one of purpose of the present invention provide a kind of biodegradable, strengthen hydroxyapatite crystal whisker/magnesium metal base composite material that body is evenly distributed, mainly as bone tissue restoration and replacement.
Two of purpose of the present invention provides a kind of preparation method of above-mentioned hydroxyapatite crystal whisker/magnesium metal base composite material, whisker enhancing magnesium base composite material enhancing body with this method preparation is evenly distributed, damage degree is little, high comprehensive performance, and technology is simple, and cost is lower.
The technical scheme that realizes the object of the invention is:
Hydroxyapatite crystal whisker/magnesium metal base composite material of the present invention is by forming as the magnesium metal of base material with as the hydroxyapatite that strengthens body, and wherein magnesium metal is pure magnesium, and purity is greater than 99wt%, and is Powdered, and granularity is less than 50 μ m; Hydroxyapatite is the whisker shape, long 2～100 μ m, and draw ratio is greater than 10; The quality percentage composition of each component of composite is: hydroxyapatite is 1～30wt%, and magnesium powder is 70～99wt%.
The draw ratio of hydroxyapatite crystal whisker can require to adjust with content according to different mechanical properties and degradation rate.When composite requires to have good plastic deformation performance and faster during degradation rate, the addition of whisker is 1～12wt%, magnesium powder is 88～99wt%; When composite required good rigidity and wearability, the addition of whisker was 12～30wt%, and magnesium powder is 70～88wt%.
The preparation method of hydroxyapatite crystal whisker/magnesium metal base composite material of the present invention is:
(1) thinning processing of magnesium powder: buy industrial magnesium powder (purity is greater than 99wt%), utilize planetary ball mill with magnesium powder particle diameter ball milling to less than 50 μ m.Ball milling adopts stainless cylinder of steel and stainless steel ball, and big bulb diameter is 10mm, and little bulb diameter is 6mm.Concrete technology: ball material mass ratio 8～9: 1, sizes of balls quantity was than 1: 5, ball milling speed 500～600rpm, 2～5 hours ball milling time.
(2) preparation of hydroxyapatite crystal whisker:, as mineralizer, adopt Hydrothermal Preparation with carbamide for obtaining draw ratio greater than 10 hydroxyapatite crystal whisker.Concrete technology: at first calcium salt and microcosmic salt aqueous solution are pressed 1.67 mixing of Ca/P atomic ratio, the carbamide that adds calcium salt and microcosmic salt gross mass (gross mass of non-calcium salt and microcosmic salt aqueous solution) 10～70wt% again, dripping nitric acid then (is water white transparency until the solution clarification, by test, this moment, pH value was about 3), solution is inserted reacting by heating in the reactor subsequently.The hydro-thermal reaction parameter is, 90 ℃ of insulations 2～5 hours down are incubated 2～5 hours under 180～220 ℃ again, furnace cooling, and the precipitation that obtains is hydroxyapatite crystal whisker.Precipitation is through distilled water and ethanol intersection filtering and washing, and last is neutral until the cleaning mixture pH value, to remove unnecessary ion all over using the ethanol filtering and washing.Whisker drying-free after the washing directly is immersed in the alcoholic solution of certain volume stand-byly, and purpose is in order to prevent that whisker from reuniting.
Content of urea can require according to the draw ratio of hydroxyapatite crystal whisker to adjust.When the carbamide addition is 10～20wt%, whisker length is less than 5 μ m, and draw ratio is about 10～12; When the carbamide addition is 20～50%, whisker length 5～50 μ m, draw ratio is greater than 20; When the carbamide addition greater than 50%, whisker length is greater than 50 μ m, the draw ratio maximum can reach 60.
(3) mixing of hydroxyapatite crystal whisker/magnesium powder: at first, take by weighing magnesium powder and hydroxyapatite crystal whisker according to each percentages of ingredients of composite, hydroxyapatite crystal whisker is mixed with the hydroxyapatite alcoholic solution of 3～5g/ml, in the hydroxyapatite alcoholic solution, add magnesium powder then, after stirring with Glass rod, inserted in the ultrasound wave ultrasonic concussion again 8～30 minutes, the slurry of mix homogeneously was put into the drying baker vacuum drying 8～12 hours;
(4) compacting sintering: with the dried batch mixing specification of packing into is in compacting-extruding steel mold of Φ 8 (extruding diameter) * Φ 20 (compacting diameter) * 70mm, and with the sealing of graphite powder fatten, prevents the oxidation and the pollution of mould batch mixing in carrying and sintering process.
The mould that batch mixing will be housed again is placed on the universal testing machine to be suppressed, pressure 40～100kN, pressurize 15～60s; After the compacting, material and mould are carried out sintering together, 400～450 ℃ of sintering temperatures, sintering time 1～5 hour;
(5) hot extrusion: the base substrate behind the sintering pushes the hydroxyapatite crystal whisker/magnesium metal base composite material that promptly is processed into bar or tubing or section bar, 360～400 ℃ of extrusion temperatures on the 600kN universal testing machine.
The invention has the beneficial effects as follows:
1) base material of the present invention adopts pure magnesium, and purity is greater than 99wt%, has avoided in the magnesium alloy commonly used poisonous alloy element to the influence of material biocompatibility;
2) enhancing body of the present invention adopts hydroxyapatite crystal whisker, compares with the graininess hydroxyapatite, can overcome the fragility of material preferably, improves fracture toughness, and does not lose excellent biological compatibility again;
3) the present invention is by the addition of adjusting hydroxyapatite crystal whisker and degradation rate and the suitable mechanical property of acquisition that major diameter is recently controlled composite;
4) hydroxyapatite crystal whisker preparation back drying-free directly mixes with magnesium powder in ethanol, effectively reduces the reunion of whisker;
5) method of ultrasound wave mixed slurry is compared with the conventional dry ball milling, has significantly reduced the extent of damage of whisker, has guaranteed the contribution of whisker to composite materials property.
6) in the sintering process; heat jointly with material compacting-extrusion die sealing back, need not the oxidation that inert atmosphere protection just can effectively prevent material, and material is from being pressed into hot extrusion process all same mould simultaneously; reduce pollution section, be particularly suitable for the preparation of biomaterial.
Biodegradable hydroxylapatite whisker-magnesium metal base composite material involved in the present invention, it strengthens, and body whisker is evenly distributed, damage degree is low, yardstick is controlled, not only guaranteed composite biological activity, but also can improve the corrosion rate and the mechanical property of composite.Preparation method is simple, and technical process is polluted few, is particularly suitable for bone tissue restoration and replacement.The magnesium base composite material that is strengthened preparation by this hydroxyapatite crystal whisker can satisfy the requirement of medical application fields such as bone tissue engineering scaffold, bone internal fixation securing member to material comprehensive mechanical property and biology performance better.
Description of drawings
The stereoscan photograph of Fig. 1-hydroxyapatite crystal whisker/magnesium metal base composite material (content of hydroxyapatite is 4wt%).
The X diffracting spectrum of Fig. 2-hydroxyapatite crystal whisker/magnesium metal base composite material (content of hydroxyapatite is 10wt%).
The specific embodiment
Introduce the present invention in detail below in conjunction with embodiment.
Biodegradable hydroxyapatite crystal whisker/magnesium metal base composite material of the present invention is formed by mixing as the magnesium metal of base material with as the hydroxyapatite that strengthens body, and wherein magnesium metal is pure magnesium, and purity is greater than 99wt%, and is Powdered, and granularity is less than 50 μ m; Hydroxyapatite is a whisker, long 2～100 μ m, and draw ratio is greater than 10; The mass percent that composite is formed is: hydroxyapatite is 1～30wt%, and magnesium powder is 70～99wt%.
The draw ratio of hydroxyapatite crystal whisker can require to adjust with content according to different mechanical properties and degradation rate.When composite requires to have good plastic deformation performance and faster during degradation rate, the addition of whisker is 1～12wt%; When composite required good rigidity and wearability, the addition of whisker was 12～30wt%.
The present invention prepares hydroxyapatite crystal whisker/magnesium metal base composite material with slurry method, is specially:
1. the thinning processing of magnesium powder: buy industrial magnesium powder (purity is greater than 99wt%), utilize planetary ball mill with magnesium powder particle diameter ball milling to less than 50 μ m.Ball milling adopts stainless cylinder of steel and stainless steel ball, and big bulb diameter is 10mm, and little bulb diameter is 6mm.Concrete technology: ball material mass ratio 8～9: 1, sizes of balls quantity was than 1: 5, ball milling speed 500～600rpm, 2～5 hours ball milling time.
2. the preparation of hydroxyapatite crystal whisker:, as mineralizer, adopt Hydrothermal Preparation with carbamide for obtaining draw ratio greater than 10 hydroxyapatite crystal whisker.Concrete technology: at first calcium salt and microcosmic salt aqueous solution are pressed 1.67 mixing of Ca/P atomic ratio, the carbamide that adds calcium salt and microcosmic salt gross mass (gross mass of non-calcium salt and microcosmic salt aqueous solution) 10～70wt% again, dripping nitric acid then (is water white transparency until the solution clarification, by test, this moment, pH value was about 3), solution is inserted reacting by heating in the reactor subsequently.The hydro-thermal reaction parameter is, insulation is 2～5 hours when being warmed up to 90 ℃, be warmed up to 180～220 ℃ again and be incubated 2～5 hours down, furnace cooling subsequently, the precipitation that obtains is hydroxyapatite crystal whisker, and precipitation is through distilled water and ethanol intersection filtering and washing, and last is all over using the ethanol filtering and washing, until the cleaning mixture pH value is neutral, to remove unnecessary ion.Whisker drying-free after the washing directly is immersed in the alcoholic solution of certain volume stand-byly, and purpose is in order to prevent that whisker from reuniting.
Content of urea can require according to the draw ratio of hydroxyapatite crystal whisker to adjust.When urea content is 10～20wt%, whisker length is less than 5 μ m, and draw ratio is about 10～12; When urea content is 20～50%, whisker length 5～50 μ m, draw ratio is greater than 20; When urea content greater than 50%, whisker length is greater than 50 μ m, the draw ratio maximum can reach 60.
3. the mixing of hydroxyapatite crystal whisker/magnesium powder.At first, according to each percentage ratio of forming of composite, take by weighing a certain amount of magnesium powder and hydroxyapatite crystal whisker.Because hydroxyapatite crystal whisker is to be immersed in the alcoholic solution, so what take by weighing is hydroxyapatite crystal whisker soak with ethanol liquid, when calculating hydroxyapatite crystal whisker weight, need the alcoholic acid quality of deduction in advance, prepare hydroxyapatite alcoholic solution (often being lower than this concentration in the time of immersion) with the concentration of 3～5g/ml again, in alcoholic solution, add a certain amount of magnesium powder then, after stirring with Glass rod, inserted in the ultrasound wave ultrasonic concussion again 8～30 minutes.The slurry of mix homogeneously was put into the drying baker vacuum drying 8～12 hours.
For the quality of the hydroxyapatite crystal whisker that accurately obtains adding in the composite, the present invention has taked following method: the first step, pre-estimate the quality of required hydroxyapatite crystal whisker.Hydrothermal condition according to the required hydroxyapatite crystal whisker of composite is prepared a hydroxyapatite crystal whisker, and through after the filtering and washing, the hydroxyapatite that is precipitated as that obtains adds small amount of ethanol.According to the characteristics of filtering and washing, as long as the condition of precipitation generative process is identical, the ratio of process sucking filtration postprecipitation and cleaning mixture is certain.Take by weighing the quality A1 of sucking filtration postprecipitation, claim dried powder behind vacuum drying, its quality is A2, and (A1-A2)/A1 compares, what can obtain the sucking filtration postprecipitation contains ethanol percentage a.According to containing ethanol percentage a, just can estimate out the amount of the required precipitation of hydroxyapatite of composite (containing ethanol) of certain proportioning.Second step, the quality of accurate Calculation hydroxyapatite crystal whisker.In composite mixed process, the ratio of ethanol and hydroxyapatite replenish to be added alcoholic solution V milliliter and is made it reach the concentration that needs, and the magnesium powder that takes by weighing quality and be B mixes with it.Take by weighing the quality C of mixed-powder after the drying.(C-B) be the quality of the hydroxyapatite crystal whisker of actual interpolation.
4. compacting sintering.With the dried batch mixing specification of packing into is in compacting-extruding steel mold of Φ 8 (extruding diameter) * Φ 20 (compacting diameter) * 70mm, and mix the thick liquid that forms with graphite powder and oils and fats by mass ratio 1: 2.5～3 mould is sealed, prevent the oxidation and the pollution of mould batch mixing in carrying and sintering process.
The mould that batch mixing is housed is placed on the universal testing machine suppresses pressure 40～100kN, pressurize 15～60s.After the compacting, material and mould are put into the batch-type furnace sintering together, 400～450 ℃ of sintering temperatures, sintering time 1～5 hour.
5. hot extrusion.The extrusion process on the 600kN universal testing machine of base substrate behind the sintering becomes bar or tubing or section bar, 360～400 ℃ of extrusion temperatures.
Introduce this preparation method below in conjunction with specific embodiment.
Embodiment 1
The first step is 100 order magnesium powder ball milling refinement on planetary ball mill of 99wt% with purity.Take by weighing magnesium powder 10.0030g and 10.0417g, put into two stainless steel jar mill respectively, put into 12 in Φ 10 big balls, 60 of Φ 6 beads in each jar simultaneously.Ball milling 2 hours, rotating speed 600rpm, two-way ball milling.After the powder ball milling is finished, put into exsiccator and preserve standby.Second step, the preparation hydroxyapatite crystal whisker.Moisture lime nitrate and dipotassium hydrogen phosphate are mixed with the aqueous solution of concentration 1M respectively, press Ca/P atomic ratio 1.67 and mix, and add the carbamide of 11wt% again, drip nitric acid then until solution clarification (pH value is about 2.97), and solution is inserted reacting by heating in the reactor subsequently.The hydro-thermal reaction parameter is, 90 ℃ of insulations 5 hours down are incubated 3 hours, furnace cooling under 200 ℃ again.The precipitation that obtains is neutral through distilled water and the washing of ethanol intersection until the cleaning mixture pH value.Whisker drying-free after the washing directly is immersed in the alcoholic solution of certain volume stand-by.SEM characterizes the signify hydroxy apatite whiskers and is about 2 μ m, and draw ratio is about 10.In the 3rd step, hydroxyapatite crystal whisker mixes with magnesium powder.Take by weighing 5.5477g magnesium powder and 0.1923g hydroxyapatite crystal whisker.Because hydroxyapatite crystal whisker is to be immersed in the alcoholic solution, so need the alcoholic acid quality of deduction in advance.In the hydroxyapatite alcoholic solution, add ethanol and make concentration reach 3.5g/ml, in alcoholic solution, add magnesium powder then, after equidirectional stirring, inserted in the ultrasound wave ultrasonic concussion again 10 minutes with Glass rod.The slurry of mix homogeneously was put into the drying baker vacuum drying 10 hours.The 4th step, the compacting of composite and sintering.Dried batch mixing is packed in compacting-extruding steel mold, and seal with the graphite powder fatten.The mould that batch mixing will be housed then is placed on the universal testing machine to be suppressed, pressure 60kN, pressurize 20s.After the compacting, material and mould are put into the batch-type furnace sintering together, 420 ℃ of sintering temperatures, sintering time 3 hours.The 5th step, the hot extrusion of composite.The extrusion process on the 600kN universal testing machine of base substrate behind the sintering becomes bar, and squeeze pressure is about 90kN, 380 ℃ of extrusion temperatures.The stereoscan photograph of hydroxyapatite crystal whisker/magnesium metal base composite material that Fig. 1 obtains for present embodiment.
Embodiment 2
The first step is 100 order magnesium powder ball milling refinement on planetary ball mill of 99.9wt% with purity.Take by weighing magnesium powder 5.6670g and 5.6580g, put into two stainless steel jar mill respectively, put into 6 in Φ 10 big balls, 30 of Φ 6 beads in each jar simultaneously.Ball milling 5 hours, rotating speed 500rpm, two-way ball milling.After the powder ball milling is finished, put into exsiccator and preserve standby.Second step, the preparation hydroxyapatite crystal whisker.Anhydrous nitric acid calcium and dipotassium hydrogen phosphate are mixed with the aqueous solution of concentration 1M respectively, press Ca/P atomic ratio 1.67 and mix, and add the carbamide of 46wt% again, drip nitric acid then until solution clarification (pH value is about 3.01), and solution is inserted reacting by heating in the reactor subsequently.The hydro-thermal reaction parameter is, 90 ℃ of insulations 3 hours down are incubated 2 hours, furnace cooling under 220 ℃ again.The precipitation that obtains is neutral through distilled water and the washing of ethanol intersection until the cleaning mixture pH value.Whisker drying-free after the washing directly is immersed in the alcoholic solution of certain volume stand-by.SEM characterizes the signify hydroxy apatite whiskers and is about 50 μ m, and draw ratio is about 25.In the 3rd step, hydroxyapatite crystal whisker mixes with magnesium powder.Take by weighing 5.6733g magnesium powder and 0.4757g hydroxyapatite crystal whisker.Because hydroxyapatite crystal whisker is to be immersed in the alcoholic solution, so need the alcoholic acid quality of deduction in advance.In the hydroxyapatite alcoholic solution, add ethanol and make concentration reach 4.8g/ml, in alcoholic solution, add magnesium powder then, after equidirectional stirring, inserted in the ultrasound wave ultrasonic concussion again 20 minutes with Glass rod.The slurry of mix homogeneously was put into the drying baker vacuum drying 10 hours.The 4th step, the compacting of composite and sintering.Dried batch mixing is packed in compacting-extruding steel mold, and seal with the graphite powder fatten.The mould that batch mixing will be housed then is placed on the universal testing machine to be suppressed, pressure 100kN, pressurize 15s.After the compacting, material and mould are put into the batch-type furnace sintering together, 450 ℃ of sintering temperatures, sintering time 3 hours.The 5th step, the hot extrusion of composite.The extrusion process on the 600kN universal testing machine of base substrate behind the sintering becomes bar, and squeeze pressure is about 95kN, 400 ℃ of extrusion temperatures.The X diffracting spectrum of hydroxyapatite crystal whisker/magnesium metal base composite material that Fig. 2 obtains for present embodiment.
The first step is 100 order magnesium powder ball milling refinement on planetary ball mill of 99.99wt% with purity.Take by weighing magnesium powder 11.504g and 11.511g, put into two stainless steel jar mill respectively, put into 12 in Φ 10 big balls, 60 of Φ 6 beads in each jar simultaneously.Ball milling 4.5 hours, rotating speed 550rpm, two-way ball milling.After the powder ball milling is finished, put into exsiccator and preserve standby.Second step, the preparation hydroxyapatite crystal whisker.Moisture lime nitrate and dipotassium hydrogen phosphate are mixed with the aqueous solution of concentration 1M respectively, press Ca/P atomic ratio 1.67 and mix, and add the carbamide of 70wt% again, drip nitric acid then until solution clarification (pH value is about 2.77), and solution is inserted reacting by heating in the reactor subsequently.The hydro-thermal reaction parameter is, 90 ℃ of insulations 3 hours down are incubated 5 hours, furnace cooling under 180 ℃ again.The precipitation that obtains is neutral through distilled water and the washing of ethanol intersection until the cleaning mixture pH value.Whisker drying-free after the washing directly is immersed in the alcoholic solution of certain volume stand-by.SEM characterizes the signify hydroxy apatite whiskers and is about 150 μ m, and draw ratio is about 60.In the 3rd step, hydroxyapatite crystal whisker mixes with magnesium powder.Take by weighing 5.5734g magnesium powder and 0.9527g hydroxyapatite crystal whisker.Because hydroxyapatite crystal whisker is to be immersed in the alcoholic solution, so need the alcoholic acid quality of deduction in advance.In the hydroxyapatite alcoholic solution, add ethanol and make concentration reach 4.2g/ml, in alcoholic solution, add magnesium powder then, after equidirectional stirring, inserted in the ultrasound wave ultrasonic concussion again 8 minutes with Glass rod.The slurry of mix homogeneously was put into the drying baker vacuum drying 12 hours.The 4th step, the compacting of composite and sintering.Dried batch mixing is packed in compacting-extruding steel mold, and seal with the graphite powder fatten.The mould that batch mixing will be housed then is placed on the universal testing machine to be suppressed, pressure 40kN, pressurize 60s.After the compacting, material and mould are put into the batch-type furnace sintering together, 400 ℃ of sintering temperatures, sintering time 5 hours.The 5th step, the hot extrusion of composite.The extrusion process on the 600kN universal testing machine of base substrate behind the sintering becomes tubing, and squeeze pressure is about 124kN, 400 ℃ of extrusion temperatures.
Embodiment 4
The first step is 100 order magnesium powder ball milling refinement on planetary ball mill of 99.99wt% with purity.Take by weighing magnesium powder 5.2090g and 5.2133g, put into two stainless steel jar mill respectively, put into 6 in Φ 10 big balls, 30 of Φ 6 beads in each jar simultaneously.Ball milling 2 hours, rotating speed 500rpm, two-way ball milling.After the powder ball milling is finished, put into exsiccator and preserve standby.Second step, the preparation hydroxyapatite crystal whisker.Anhydrous nitric acid calcium and dipotassium hydrogen phosphate are mixed with the aqueous solution of concentration 1M respectively, press Ca/P atomic ratio 1.67 and mix, and add the carbamide of 70wt% again, drip nitric acid then until solution clarification (pH value is about 3.00), and solution is inserted reacting by heating in the reactor subsequently.The hydro-thermal reaction parameter is, 90 ℃ of insulations 2 hours down are incubated 3 hours, furnace cooling under 200 ℃ again.The precipitation that obtains is neutral through distilled water and the washing of ethanol intersection until the cleaning mixture pH value.Whisker drying-free after the washing directly is immersed in the alcoholic solution of certain volume stand-by.SEM characterizes the signify hydroxy apatite whiskers and is about 150 μ m, and draw ratio is about 60.In the 3rd step, hydroxyapatite crystal whisker mixes with magnesium powder.Take by weighing 5.6670g magnesium powder and 1.4283g hydroxyapatite crystal whisker.Because hydroxyapatite crystal whisker is to be immersed in the alcoholic solution, so need the alcoholic acid quality of deduction in advance.In the hydroxyapatite alcoholic solution, add ethanol and make concentration reach 3.2g/ml, in alcoholic solution, add magnesium powder then, after equidirectional stirring, inserted in the ultrasound wave ultrasonic concussion again 20 minutes with Glass rod.The slurry of mix homogeneously was put into the drying baker vacuum drying 10 hours.The 4th step, the compacting of composite and sintering.Dried batch mixing is packed in compacting-extruding steel mold, and seal with the graphite powder fatten.The mould that batch mixing will be housed then is placed on the universal testing machine to be suppressed, pressure 80kN, pressurize 40s.After the compacting, material and mould are put into the batch-type furnace sintering together, 450 ℃ of sintering temperatures, sintering time 3 hours.The 5th step, the hot extrusion of composite.The extrusion process on the 600kN universal testing machine of base substrate behind the sintering becomes bar, and squeeze pressure is about 102kN, 360 ℃ of extrusion temperatures.
Claims (6)
1. hydroxyapatite crystal whisker/magnesium metal base composite material is characterized in that: described composite is by forming as the magnesium metal of base material with as the hydroxyapatite that strengthens body, and wherein magnesium metal is pure magnesium, and is Powdered; Hydroxyapatite is the whisker shape, long 2～100 μ m, and draw ratio is greater than 10; The quality percentage composition of each component of composite is: hydroxyapatite is 1～30wt%, and magnesium powder is 70～99wt%;
The preparation process of this composite is:
(1) thinning processing of magnesium powder: pure magnesium powder particle diameter is ground to less than 50 μ m;
(2) preparation of hydroxyapatite crystal whisker: at first calcium salt and microcosmic salt aqueous solution are pressed 1.67 mixing of Ca/P atomic ratio, the carbamide that adds calcium salt and microcosmic salt gross mass 10～70wt% again, dripping nitric acid then clarifies until solution, solution is inserted reacting by heating in the reactor subsequently, wherein 90 ℃ are incubated 2～5 hours down, 180～220 ℃ are incubated 2～5 hours down, furnace cooling, the precipitation that obtains is hydroxyapatite crystal whisker, precipitation is through distilled water and ethanol intersection filtering and washing, last is neutral all over using the ethanol filtering and washing until the cleaning mixture pH value, and the whisker after the washing directly is immersed in the alcoholic solution stand-by;
(3) mixing of hydroxyapatite crystal whisker/magnesium powder: at first, take by weighing magnesium powder and hydroxyapatite crystal whisker according to each percentages of ingredients of composite, hydroxyapatite crystal whisker is mixed with the hydroxyapatite alcoholic solution of 3～5g/ml, in the hydroxyapatite alcoholic solution, add magnesium powder then, after stirring with Glass rod, inserted in the ultrasound wave ultrasonic concussion again 8～30 minutes, the slurry of mix homogeneously was put into the drying baker vacuum drying 8～12 hours;
(4) compacting sintering: dried batch mixing is packed in compacting-extruding steel mold, the mould that batch mixing is housed is placed on the universal testing machine suppresses pressure 40～100kN, pressurize 15～60s; After the compacting, material and mould are carried out sintering together, 400～450 ℃ of sintering temperatures, sintering time 1～5 hour;
(5) hot extrusion: the base substrate behind the sintering pushes the hydroxyapatite crystal whisker/magnesium metal base composite material that promptly is processed into bar or tubing or section bar, 360～400 ℃ of extrusion temperatures on the 600kN universal testing machine.
2. hydroxyapatite crystal whisker/magnesium metal base composite material according to claim 1 is characterized in that: described hydroxyapatite is 1～12wt%, and magnesium powder is 88～99wt%.
3. hydroxyapatite crystal whisker/magnesium metal base composite material according to claim 1 is characterized in that: described hydroxyapatite is 12～30wt%, and magnesium powder is 70～88wt%.
4. hydroxyapatite crystal whisker/magnesium metal base composite material according to claim 1 is characterized in that: described magnesium metal purity is greater than 99wt%, and granularity is less than 50 μ m.
5. hydroxyapatite crystal whisker/magnesium metal base composite material according to claim 1, it is characterized in that: when the thinning processing of Composite Preparation step the (1) step magnesium powder, utilize planetary ball mill with magnesium powder particle diameter ball milling to less than 50 μ m, ball milling adopts stainless cylinder of steel and stainless steel ball, and big bulb diameter is 10mm, and little bulb diameter is 6mm, ball material mass ratio 8～9: 1, sizes of balls quantity is than 1: 5, ball milling speed 500～600rpm, 2～5 hours ball milling time.
6. hydroxyapatite crystal whisker/magnesium metal base composite material according to claim 1, it is characterized in that: when Composite Preparation step the (4) goes on foot compacting sintering, dried batch mixing pack in compacting-extruding steel mold into back with graphite powder and the sealing of greasy mixture, and graphite powder mixes the formation thick liquid with oils and fats by mass ratio 1: 2.5～3.
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| CN103585677B (en) * | 2013-10-30 | 2015-09-09 | 四川大学 | A kind of HA micro-nano whisker reinforcement calcium phosphate ceramic material and its preparation method and application |
| CN103599561B (en) * | 2013-11-07 | 2015-08-19 | 同济大学 | A kind of preparation method of magnesium alloy/hydroxyapatite composite |
| CN104623734B (en) * | 2015-01-30 | 2016-11-02 | 太原理工大学 | A kind of fast preparation method of magnesium/hydroxyapatite degradable composite material |
| CN104928510B (en) * | 2015-06-30 | 2017-05-17 | 西安交通大学 | Preparation method of fine-grain Mg-based composite material comprising AlN (aluminum nitride) particles |
| CN106282855A (en) * | 2016-09-28 | 2017-01-04 | 广州凯耀资产管理有限公司 | A kind of inorganic crystal whisker strengthens magnesium base composite material and preparation method thereof |
| CN106268614B (en) * | 2016-10-18 | 2019-08-13 | 南京信息工程大学 | A kind of preparation method of magnesium-hydroxyapatite adsorbent |
| CN110231356B (en) * | 2019-05-27 | 2020-07-28 | 西安交通大学 | Method for improving hydroxyapatite degradability by electron irradiation |
| CN114478040B (en) * | 2022-01-24 | 2023-06-30 | 西安卓恰新材料科技有限公司 | Modified bioactive ceramic powder and application thereof |
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