CN105770997A - Biological material for artificial joint, preparing method thereof and preparation of prosthesis material - Google Patents

Biological material for artificial joint, preparing method thereof and preparation of prosthesis material Download PDF

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Publication number
CN105770997A
CN105770997A CN201610124555.6A CN201610124555A CN105770997A CN 105770997 A CN105770997 A CN 105770997A CN 201610124555 A CN201610124555 A CN 201610124555A CN 105770997 A CN105770997 A CN 105770997A
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China
Prior art keywords
strontium
artificial joint
biomaterial
calcium polyphosphate
doped calcium
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CN201610124555.6A
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Chinese (zh)
Inventor
余喜讯
刘景望
杨旭
秦欢欢
彭红
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Sichuan University
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Sichuan University
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Priority to CN201610124555.6A priority Critical patent/CN105770997A/en
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/46Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54Biologically active materials, e.g. therapeutic substances
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/412Tissue-regenerating or healing or proliferative agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/24Materials or treatment for tissue regeneration for joint reconstruction

Abstract

The invention discloses a biological material for an artificial joint, a preparing method thereof and preparation of a prosthesis material.Ultra high molecular weight polyethylene with the molecular weight not smaller than 1000000 is used as a matrix, strontium-doped calcium polyphosphate serving as a reinforcing material of an artificial joint assembly is used for filling modification to obtain a composite material namely the biological material, the mass percentage of strontium-doped calcium polyphosphate in the composite material is 5-10%, and the molar ratio of Sr/Ca in strontium-doped calcium polyphosphate is (6-9):(94-91).The preparing method includes the steps that prepared strontium-doped calcium polyphosphate is ground into power with the particle size of 20-50 micrometers, and then the strontium-doped calcium polyphosphate powder and ultra high molecular weight medical polyethylene powder are put into a ball mill to be mixed to obtain the biological material for the artificial joint.The biological material for the artificial joint can improve mechanical performance of a prosthesis assembly, has a partial medicine treatment effect on bone resorption around a prosthesis and is a biological material which can be used clinically for the artificial joint.

Description

The preparation of artificial joint biomaterial and preparation method thereof and prosthetic material
Technical field
The present invention relates to artificial joint material technical field, specifically, relate to a kind of artificial joint biomaterial And preparation method thereof, and the method being prepared artificial joint prosthesis material by artificial joint biomaterial.
Technical background
Along with developing rapidly of social economy and medical condition, the average life of modern significantly improves, social senilization Aggravation, osteoarthritis patients presents the trend of average annual growth.Substantial amounts of patient needs artificial joint to perform the operation, the most effectively Prophylactic treatment joint disease, it has also become the problem that people pay much attention to.Total joint replacement includes total hip replacement Art and total knee arthroplasty, be the downright bad effective means with severe joint damage for the treatment of human synovial, can effectively alleviate The pain of patient and reconstruction function of joint.Joint replacement originates from the U.S., is developed so far the history of the nearlyest two a century, Its demand is at present in zooming trend.2007, U.S.'s prosthetic replacement's market capitalisation reached 5,900,000,000 Dollar, it is contemplated that it was up to 12,400,000,000 dollars by 2017, and the potential annual requirement of China reaches about 3,000,000 sets. 2010, China's hip prosthesis consumption figure was about 180,000 sets, in recent years remains the annual rate of growth of 15-20%.Additionally Compared with western countries, the age distribution of China patient more rejuvenation, joint is implanted to the combination property of prosthetic material Have higher requirement with service life.
Aseptic loosening is to affect the late result of artificial joint replacement and cause the most important factor of its failure, and it is not Only hinder popularization and application and the development further of artificial joint, and have a strong impact on the life of joint disease patient Bioplasm amount.Find effective means of prevention of aseptic loosening, the generation of suppression aseptic loosening and prolongation artificial joint to make The task that this research field is extremely urgent is become with the life-span.From the pathogenesis analysis of aseptic loosening, current preventing and treating Means mainly divide two aspects, and one is the mechanical performance improving prosthesis assembly;Two is Drug therapy, is promoted by medicine Bone formation, suppresses bone resorption.
Taking a broad view of these prevention and controls of prior art, they are all pathogenetic just for aseptic loosening of prosthesis In a certain respect, role has certain limitation, and its effect is the most preferable.Therefore, a kind of new life is found Thing active material, is allowed to improve the mechanical performance of prosthesis assembly, Periprosthetic bone resorption can be played topical remedy again Therapeutical effect, reaches dual preventing and treating modified effect, and the preventing and treating for aseptic loosening of prosthesis provides a kind of new combining Conjunction property solution.
Summary of the invention
For the present situation of artificial joint biomaterials art of prior art with not enough, first purpose of the present invention is A kind of mechanical performance that can improve prosthesis assembly is provided, Periprosthetic bone resorption can be played again topical medications and make With, there is the artificial joint biomaterial of dual preventing and treating modified effect;Second purpose is to provide one and prepares this people Work closes the method saving biomaterial;3rd purpose is to provide this artificial joint biomaterial a kind of and prepares work pass The method of joint prosthetic material.
For first goal of the invention of the present invention, the artificial joint biomaterial that the present invention provides, for one to divide It is matrix that son amount is not less than the ultra-high molecular weight polyethylene (UHMWPE) of 1,000,000, through increasing as prosthetic joint component Composite that the strontium-doped calcium polyphosphate (SCPP) of strong material is filling-modified, strontium-doped calcium polyphosphate is in the composite Mass content is 5%-10%, and the Sr/Ca mol ratio in described strontium-doped calcium polyphosphate is (6-9): (94-91).
In technique scheme, described strontium-doped calcium polyphosphate preferentially selects the powder of particle diameter 20-50 μm, described super High molecular weight polyethylene preferentially selects medical grade ultra-high molecular weight polyethylene powder.
For second goal of the invention of the present invention, the side preparing described artificial joint biomaterial that the present invention provides Method, mainly includes following operation:
(1) according to Sr/Ca mol ratio 6-9:94-91, the strontium carbonate of powder and the mixture of calcium carbonate are added phosphorus In acid solution, stirring until white powder is completely dissolved in solution, then sealing and standing is no less than 8 hours, afterwards will Solution is transferred in Rotary Evaporators, and evacuation crystallizes, and obtains the mixture of strontium biphosphate and dalcium biphosphate, uses Excess phosphoric acid in ethanol eccysis mixture, being washed by mixture to cleaning mixture is neutrality, and the dried porcelain crucible that loads is put into Carrying out twice high temperature sintering process in Muffle furnace, i.e. preparing strontium molar content is 6%-9% strontium-doped calcium polyphosphate;
(2) after the strontium-doped calcium polyphosphate of strontium molar content 6%-9% tentatively being ground to form granule, then grind with ball milling instrument Obtain strontium-doped calcium polyphosphate powder;
(3) the described strontium-doped calcium polyphosphate powder of formula ratio is put with ultra-high molecular weight polyethylene medical polyethylene powder Enter in ball mill and mix, i.e. prepare artificial joint biomaterial.
In technique scheme, the phosphoric acid that described phosphoric acid solution preferentially selects concentration to be 1.5mol/L-2.5mol/L Solution;Further, described phosphoric acid solution uses concentration to be 0.4mol-0.6mol strong phosphoric acid and deionized water are prepared Become.
In technique scheme, after step (1) transfers the solution in Rotary Evaporators, preferential selection water-bath is true Empty pump is evacuated to 0.07-0.09MPa;The rotation speed of described Rotary Evaporators is 80-100 rev/min;Described vacuum The bath temperature of pump is 50 DEG C-80 DEG C.
In technique scheme, the mixture of the dalcium biphosphate after washing and strontium biphosphate is loaded porcelain dish, excellent First select infrared lamp to irradiate and be dried process.
In technique scheme, dalcium biphosphate and strontium biphosphate mixture after drying are carried out in Muffle furnace Described twice high temperature sintering, its for the first time high temperature sintering be to be warming up to 8 DEG C-10 DEG C/min from room temperature 450 DEG C-600 DEG C, it is incubated 8 hours-10 hours, then heats to 1000 DEG C-1200 DEG C, be incubated 40 minutes-70 Quench after minute;Block imitation frosted glass after high temperature sintering is by quenching for the second time is warming up to 8 DEG C-10 DEG C/min from room temperature 700 DEG C-900 DEG C, take out after insulation 4-6h, i.e. prepare the strontium-doped calcium polyphosphate obtaining 6%-9%.
In technique scheme, strontium biphosphate and biphosphate calcium compound institute in first time high-temperature sintering process The quenching carried out, preferentially takes to pour rapidly the molten material taken out from Muffle furnace into ice cube that deionized water is frozen into In carry out Quenching Treatment.
In technique scheme, after the strontium-doped calcium polyphosphate of strontium molar content 6%-9% grinds with ball milling instrument, sieve sieve Take the strontium-doped calcium polyphosphate powder of particle diameter 20-50 μm.
For the 3rd goal of the invention of the present invention, what the present invention provided prepares people with aforementioned artificial joint biomaterial The method of work materials for joint prosthesis, is described artificial joint biomaterial to join artificial joint prosthesis mould send into Moulding press, applies 8MPa-12MPa molding pressure to described artificial joint biomaterial at 180 DEG C-220 DEG C and protects Hold 30 minutes-50 minutes, finally under 8Mpa-12MPa molding pressure, be cooled to room temperature, i.e. prepare work articular prosthesis material Material.
Further scheme, described artificial joint biomaterial joins artificial joint prosthesis mould and sends into moulding press, At non-pressurized situation is prior to 180 DEG C-220 DEG C, preheats 10min-20min, discharges the bubble in biomaterial, so After then at 8MPa-12MPa molding pressure, mold 30 minutes-50 minutes at 180 DEG C-220 DEG C, finally at 8Mpa-12MPa It is cooled to room temperature under molding pressure.
In the research complete process preparing artificial joint biomaterial, inventor finds in early-stage Study, mixes strontium Calcium polyphosphate has good biocompatibility, meets the requirement as bone tissue engineering stent material, can be to a certain degree The intensity of upper raising skeleton and toughness, and osteoblastic propagation and suppression bone resorption can be promoted, accelerate Bone Defect Repari, And SCPP effect with strontium content as 6%-9% is best.
UHMWPE is current most widely used cotyla material, it and the coefficient of friction of metal joint head and human body hip The coefficient of friction in joint is close, and it is joined assistant formula formula the most extensively UHMWPE material and has good wear resistence, excellent Mechanical performance, corrosion resistance and biocompatibility and the physiological inertia of excellence, so, inventor selects UHMWPE As artificial joint material.But, polyethylene mortar cup is still that the fragile link of Combined type joint prosthese.Work as polyethylene When mortar cup occurs normal or abnormal activity with adjacent metal or ceramic articulation head surface, its relatively soft characteristic determines this Its part is the most easily worn.Ultra-high molecular weight polyethylene abrasive dust accounts for the 70% 1 of artificial joint prosthesis total abrasive dust amount 90%.Research shows, ultra-high molecular weight polyethylene abrasive dust has the higher Periprosthetic bone that causes than metal filings and dissolves Effect, be the key factor causing prosthese aseptic loosening.
The present invention is using UHMWPE as the matrix material of artificial joint biomaterial, with strontium molar content as 6%-9% SCPP is as the reinforcement filler of UHMWPE artificial joint material, and prepared artificial joint biomaterial is from two sides In the face of ultra-high molecular weight polyethylene artificial joint prosthesis wear improves: one is to improve abrasion resistance properties, reduce The generation of wear particle;Two is to make the wear particle produced have biological activity and pharmaceutically active (increase skeletonization Cytoactive, promotes skeletonization;Suppression osteoclast activity;Alleviate the inflammatory reaction caused by abrasive dust), suppress or slow Solve the generation of aseptic loosening, be well suited for artificial joint material.And its preparation process is simple, technology is less demanding, It is easily achieved industrialization.
Accompanying drawing explanation
Accompanying drawing 1 is that electron-microscope scanning wear surface used after dry friction by several artificial joint prosthesis materials prepared by the present invention Electronic Speculum figure, wherein:
A is UHMWPE shape appearance figure of wear surface under the conditions of SEM amplifies 25 times;
B is UHMWPE shape appearance figure of wear surface under the conditions of SEM amplifies 50 times;
C is UHMWPE shape appearance figure of wear surface under the conditions of SEM amplifies 200 times;
D is 5%SCPP/UHMWPE shape appearance figure of wear surface under the conditions of SEM amplifies 25 times;
E is 5%SCPP/UHMWPE shape appearance figure of wear surface under the conditions of SEM amplifies 50 times;
F is 5%SCPP/UHMWPE shape appearance figure of wear surface under the conditions of SEM amplifies 200 times;
G is 10%SCPP/UHMWPE shape appearance figure of wear surface under the conditions of SEM amplifies 25 times;
H is 10%SCPP/UHMWPE shape appearance figure of wear surface under the conditions of SEM amplifies 50 times;
I is 10%SCPP/UHMWPE shape appearance figure of wear surface under the conditions of SEM amplifies 200 times.
Accompanying drawing 2-1 is that relatively (* represents and compares breeding ratio during MG63 and variety classes wear particle compound criteria 1d Compare significant difference, n=6) block diagram.
Accompanying drawing 2-2 is that relatively (* represents and compares breeding ratio during MG63 and variety classes wear particle compound criteria 2d Compare significant difference, n=6) block diagram.
Accompanying drawing 2-3 is that relatively (* represents and compares breeding ratio during MG63 and variety classes wear particle compound criteria 4d Compare significant difference, n=6) block diagram.
Accompanying drawing 3 is the hardness profile of SCPP/UHMWPE composite under different SCPP content.
Accompanying drawing 4 is the impact strength curve figure of SCPP/UHMWPE composite under different SCPP content.
Accompanying drawing 5 is the wear rate curve chart of SCPP/UHMWPE composite under different SCPP content.
Detailed description of the invention
Provide the detailed description of the invention of the present invention below by embodiment, present disclosure is remake the most in detail Explanation.But it should be strongly noted that this should be interpreted as that protection scope of the present invention is only limitted to example, on the contrary It is that all technology realized based on present disclosure should belong to protection scope of the present invention.
In following instance, unless otherwise indicated, involved percentage ratio is mass percent, and involved number is Mass fraction.
1. the preparation embodiment of artificial joint biomaterial and artificial joint prosthesis material
It is that 9:91 (total mole number is 0.2mol) weighs strontium carbonate and calcium carbonate powder by Sr/Ca mol ratio;Will 0.5mol strong phosphoric acid and deionized water add 250mL volumetric flask, are made into the phosphate standard solution of 2mol/L;By carbonic acid The mixture of strontium and calcium carbonate adds in the phosphoric acid solution prepared, and stirs until white powder is completely dissolved, so in solution After seal up preservative film and stand overnight (12 hours).Transfer the solution in Rotary Evaporators, be pumped into very with vacuum pump Empty (about 70 DEG C;Rotating speed 100 revs/min;Vacuum: 0.07MPa), crystallization obtains strontium biphosphate and di(2-ethylhexyl)phosphate The mixture of hydrogen calcium;Wash out in mixture the phosphoric acid of excess with ethanol, cyclic washing and sucking filtration, until cleaning mixture in Property, the mixture of dalcium biphosphate and strontium biphosphate is loaded porcelain dish, infrared lamp is the most standby;By biphosphate Strontium loads porcelain crucible with the mixture of dalcium biphosphate, puts in Muffle furnace and calcines, from room temperature with 8 DEG C-10 DEG C/min It is warming up to about 450 DEG C, is incubated about 10 hours.Then about 1100 DEG C are risen to, after being incubated 70 minutes, by molten Material takes out to pour into rapidly in the ice cube that deionized water is frozen into from Muffle furnace and quenches;For the second time high temperature sintering be by Block SCPP imitation frosted glass after quenching is raised to about 900 DEG C from room temperature with 10 DEG C/min heating rate, is incubated about 4 hours Rear taking-up, has i.e. prepared 9%SCPP material.
After 9%SCPP material is tentatively ground to form granule, then it is ground with ball milling instrument, specifically comprises the following steps that two Ball grinder is respectively charged into same amount of material to be ground every time, ball grinder is loaded ball mill, under the conditions of 10-20Hz Grind 30-50min.Sieving after grinding, it is standby to obtain the powder of particle diameter 20-50 μm.
Being mixed in ball mill with pure UHMWPE powder by the SCPP powder prepared, obtaining mass fraction is 0%, the SCPP/UHMWPE powder of 5%, 10%, 20% and 30%, is artificial joint biomaterial to be prepared.
Obtained artificial joint biomaterial is joined artificial joint prosthesis mould and sends into moulding press, be not pressurized In the case of in 200 DEG C preheat 20min, make bubble fully discharge, then apply 12MPa molding pressure, in 200 DEG C Keep 1 hour.Last cooling in room temperature under 12MPa molding pressure, takes out from prosthese mould, i.e. obtains artificial Materials for joint prosthesis sample.
2, artificial joint biomaterial testing performance index embodiment
(1) hardness test embodiment
Hardness is an important indicator of reflection material wear-resistant performance, and hardness is the highest, and its corresponding abrasion resistance properties is the best. The hardness measurement of SCPP/UHMWPE composite prepared by embodiment is prepared by above-mentioned artificial joint biomaterial, adopts The hardness of molding sample is measured with Shore durometer.Fig. 3 is SCPP/UHMWPE composite wood under different SCPP content The hardness curve of material.
As seen from Figure 3, the hardness of SCPP/UHMWPE composite increases with the increase of SCPP component ratio. SCPP can obviously improve the case hardness of UHMWPE, and with the increase of SCPP addition, the microhardness of composite increases. This variation tendency is relatively mild, after SCPP content reaches 10% when SCPP content is less than 10% (mass fraction) Long-term change trend is obvious.This is because SCPP microgranule has the highest elastic modelling quantity, hardness is hard much larger than UHMWPE's Degree, adds SCPP granule and is evenly dispersed among SCPP/UHMWPE surface and matrix so that the bullet of composite Property modulus dramatically increases, so that the hardness of SCPP/UHMWPE is improved significantly with the increase of SCPP granule density. The hardness of SCPP/UHMWPE composite is the biggest, and the anti-wear performance of illustrative material is the best, more can reduce wear particle Produce.
(2) impact strength testing example
As artificial joint biomaterial, the impact strength of tissue is a highly important index.To above-mentioned people Work pass is saved biomaterial and is prepared the hardness measurement of SCPP/UHMWPE composite prepared by embodiment, uses pendulum Shock machine measures.Fig. 4 is the impact strength curve chart of SCPP/UHMWPE composite under different SCPP content.
As seen from Figure 4, the ultra-high molecular weight polyethylene impact strength after SCPP filling, with the increasing of filer content Add and declined.After content is more than 10%, impact strength suppression ratio is more apparent.This is because proportion of filler increases When adding to a certain extent, due to trickle SCPP granule surface can and surface tension bigger, and SCPP with Combination between UHMWPE two kinds not homophase can not reach entirely without gap, and too much SCPP granule is at UHMWPE Matrix can affect its seriality on the contrary, the compartmentation of matrix is increased, and becomes stress concentration point, cause punching Hit toughness to decline.Thus when adding the friction and wear behavior that SCPP granule improves UHMWPE, SCPP ratio is unsuitable excessive.
(3) friction and wear behavior testing example
Friction and wear behavior test is the important indicator intuitively reflecting material wear-resistant performance, the lowest explanation of wear rate The anti-wear performance of material is the best.Above-mentioned artificial joint biomaterial is prepared the SCPP/UHMWPE prepared by embodiment The wear rate of composite is measured, and uses MM-200 type abrasion tester to be measured.Fig. 5 is different SCPP content The wear rate curve chart of lower SCPP/UHMWPE composite.
As seen from Figure 5, SCPP granule can improve the wearability of UHMWPE.SCPP content in the range of 0%-20%, The wear extent of SCPP/UHMWPE declines rapidly with the increase of SCPP content.This is because, the on the one hand chi of SCPP granule Very little small, can be evenly dispersed in UHMWPE matrix, in wear process, under the effect of normal pressure, SCPP Granule embeds in UHMWPE matrix, decreases the chance that UHMWPE is directly worn and torn, thus improves UHMWPE's Wearability;On the other hand, add SCPP granule and can improve the case hardness of material, thus improve its wear resistance, Result meets the rule between the hardness described by tribology ArHArd formula and wear rate.The raising of case hardness strengthens SCPP/UHMWPE composite, to the ditch dug with a plow resistance to the hard micro-bulge in mill surface, causes the anti-ditch dug with a plow of material and viscous Ability of improves, and result obtains the wear rate lower than pure UHMWPE material.
From micro-hardness experiments result it will be seen that the hardness of SCPP/UHMWPE composite is with the increase of SCPP content And increase, but the result of frictional experiment display SCPP filler is when addition is more than 20%, and polishing machine starts to be deteriorated. Therefore, add SCPP filler and should take into full account the suitably matching effect such as case hardness, wear resistance and impact strength. The requirement to implant impact strength of the case hardness of bond material, wear resistance and artificial joint material, when When SCPP filer content is in the range of 5%-10%, relatively good to the modified effect of UHMWPE, time in the range of 6%-9% More preferably.
(4) osteoblast and wear particle compound criteria embodiment
The research to osteoblastic proliferation situation of the wear particle of SCPP/UHMWPE composite, for artificial joint With the most particularly significant for biomaterial.Osteoblast is osteoplastic chief functional cells, between it and osteoclast There is dynamic equilibrium, maintain bone remodeling, keep normal bone amount.Wear particle, can be directly to osteoblastic effect Have influence on the dynamic equilibrium between Periprosthetic bone formation and bone resorption, depositing of wear particle, on the one hand can direct shadow Ring osteoblast vigor, on the other hand can affect Periprosthetic by stimulating the effect secreting a series of cytokine Bone remoulding.
Proliferative conditions such as accompanying drawing 2-1, Fig. 2-2 and Fig. 2-3 of osteoblast MG63 and different wear particle compound criteria Shown in.As seen from the figure, along with the prolongation of compound criteria time, all containing SCPP granule group ability of cell proliferation It is above UHMWPE group (P < 0.05).Illustrate SCPP/UHMWPE composite wear particle can with promoting bone growing, It is beneficial to Periprosthetic bone remoulding, there is pharmaceutically active.
(5) in vitro study that osteoblast OPG, RANKL mRNA and protein expression are affected by different wear particles is real Execute example
During the aseptic loosening of prosthese, numerous cells is had to participate in.The release of the numerous cytokine of simultaneous, Wherein, the balance of osteoprotegerin (OPG) and receptor activator of the nuclear factor-κappaB ligand (RANKL) is thin at broken bone Pivotal role is played during born of the same parents' activation and bone resorption.Above-mentioned artificial joint biomaterial is prepared prepared by embodiment SCPP/UHMWPE worn composite granule to osteoblast OPG, RANKL mRNA and the measurement of protein expression, Elisa (ELISA) and real-time fluorescence quantitative RT-PCR can be used to measure.
Use ELISA (ELISA) to the osteoblast with different materials wear particle compound criteria OPG and RANKL in MG63 culture fluid detects in the expression of protein level, simultaneously by MTT testing result pair The expressing quantity obtained is corrected, and show that osteoblast secretes OPG/RANKL ratio, and result shows, contains In SCPP wear particle group, the expressing quantity of cell OPG is higher than UHMWPE matched group (P < 0.05);Meanwhile, divide Secrete the ratio of OPG/RANKL higher than UHMWPE matched group (P < 0.05) (P < 0.05).
Use the Real-Time Fluorescent Quantitative PCR Technique pair osteoblast MG63's with different materials wear particle compound criteria OPG and RANKL detects in the expression of mRNA level in-site and calculates, and result is as shown in table 5-5, and * represents this group 's△△CtThere is significant difference in value and UHMWPE matched group.
The relative expression quantity (N=4) of table 1 OPG and RANKL mRNA
Test result indicate that, be above UHMWPE containing osteoblast OPG mrna expression amount in SCPP wear particle group Matched group;Meanwhile, the ratio containing SCPP granule group OPG and RANKL relative expression quantity is above UHMWPE matched group (P < 0.05), thus strengthen bone formation and suppression bone resorption, it is shown that modified material can to artificial joint without Bacterium property loosens and plays the effect that Drug therapy is identical.

Claims (10)

1. an artificial joint biomaterial, it is characterised in that for a kind of with molecular weight be not less than 1,000,000 super High molecular weight polyethylene is that matrix warp can be filling-modified as the strontium-doped calcium polyphosphate of prosthetic joint component reinforcing material Composite, described strontium-doped calcium polyphosphate mass content in the composite is 5%-10%, in strontium-doped calcium polyphosphate Sr/Ca mol ratio be 6-9:94-91.
Artificial joint biomaterial the most according to claim 1, it is characterised in that described in mix strontium polyphosphoric acid Calcium is the powder of particle diameter 20-50 μm, and described ultra-high molecular weight polyethylene is medical grade ultra-high molecular weight polyethylene Powder.
3. the preparation method of artificial joint biomaterial described in claim 1 or 2, it is characterised in that include following Operation:
(1) according to Sr/Ca mol ratio 6-9:94-91, the strontium carbonate of powder and the mixture of calcium carbonate are added phosphorus In acid solution, stirring until white powder is completely dissolved in solution, then sealing and standing is no less than 8 hours, afterwards will Solution is transferred in Rotary Evaporators, and evacuation crystallizes, and obtains the mixture of strontium biphosphate and dalcium biphosphate, uses Excess phosphoric acid in ethanol eccysis mixture, being washed by mixture afterwards to cleaning mixture is neutrality, loads porcelain crucible after drying Putting into and carry out twice high temperature sintering process in Muffle furnace, i.e. preparing strontium molar content is 6%-9% strontium-doped calcium polyphosphate;
(2) after the strontium-doped calcium polyphosphate of strontium molar content 6%-9% tentatively being ground to form granule, then grind with ball milling instrument It is 20-50 μm strontium-doped calcium polyphosphate powder to particle diameter;
(3) the described strontium-doped calcium polyphosphate powder of formula ratio is put with ultra-high molecular weight polyethylene medical polyethylene powder Enter in ball mill and mix, i.e. prepare artificial joint biomaterial.
The preparation method of artificial joint biomaterial the most according to claim 3, it is characterised in that described phosphorus Acid solution is the phosphoric acid solution of concentration 1.5mol/L-2.5mol/L, is the strong phosphoric acid of 0.4mol-0.6mol by concentration It is configured to deionized water.
The preparation method of artificial joint biomaterial the most according to claim 3, it is characterised in that step (1), after transferring the solution in Rotary Evaporators, it is evacuated to 0.07-0.09MPa, described rotation with water-bath vacuum pump The rotation speed turning evaporimeter is 80-100 rev/min, and the bath temperature of described vacuum pump is 50 DEG C-80 DEG C.
The preparation method of artificial joint biomaterial the most according to claim 3, it is characterised in that will wash Dalcium biphosphate and the mixture of strontium biphosphate after washing load porcelain dish, irradiate with infrared lamp and are dried process.
The preparation method of artificial joint biomaterial the most according to claim 3, it is characterised in that described First time high temperature sintering in twice high temperature sintering, is to be warming up to 450 DEG C-600 DEG C from room temperature with 8 DEG C-10 DEG C/min, It is incubated 8 hours-10 hours, then heats to 1000 DEG C-1200 DEG C, quench after being incubated 40 minutes-70 minutes;The Secondary high-temperature sintering is that the block imitation frosted glass after quenching is warming up to 700 DEG C-900 DEG C from room temperature with 8 DEG C-10 DEG C/min, protects Take out after temperature 4-6h, i.e. prepare the strontium-doped calcium polyphosphate obtaining 6%-9%.
The preparation method of artificial joint biomaterial the most according to claim 7, it is characterised in that phosphoric acid Dihydro strontium and the described quenching in first time high-temperature sintering process of the biphosphate calcium compound, be to take from Muffle furnace The molten material of middle taking-up is poured into rapidly and is carried out Quenching Treatment in the ice cube that deionized water is frozen into.
The preparation method of artificial joint biomaterial the most according to claim 3, it is characterised in that strontium rubs After the strontium-doped calcium polyphosphate of you content 6%-9% grinds with ball milling instrument, the strontium-doped calcium polyphosphate of screening particle diameter 20-50 μm Powder.
10. the method that artificial joint prosthesis material prepared by artificial joint biomaterial described in claim 1 or 2, its It is characterised by, described artificial joint biomaterial is joined artificial joint prosthesis mould and sends into moulding press, in At 180 DEG C-220 DEG C, described artificial joint biomaterial applied 8MPa-12MPa molding pressure and keep 30 minutes -50 minutes, finally under 8Mpa-12MPa molding pressure, it is cooled to room temperature, i.e. prepares artificial joint prosthesis material.
CN201610124555.6A 2016-03-04 2016-03-04 Biological material for artificial joint, preparing method thereof and preparation of prosthesis material Pending CN105770997A (en)

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