CN108378929A - With locator markers and preparation method thereof made of degradable metal - Google Patents
With locator markers and preparation method thereof made of degradable metal Download PDFInfo
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- CN108378929A CN108378929A CN201810324357.3A CN201810324357A CN108378929A CN 108378929 A CN108378929 A CN 108378929A CN 201810324357 A CN201810324357 A CN 201810324357A CN 108378929 A CN108378929 A CN 108378929A
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- China
- Prior art keywords
- locator markers
- magnesium
- locator
- markers
- silk
- Prior art date
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Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 12
- 239000002184 metal Substances 0.000 title claims abstract description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000011777 magnesium Substances 0.000 claims abstract description 40
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 40
- 239000003550 marker Substances 0.000 claims abstract description 34
- 229910000861 Mg alloy Inorganic materials 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000015556 catabolic process Effects 0.000 claims abstract description 15
- 238000006731 degradation reaction Methods 0.000 claims abstract description 15
- 238000004804 winding Methods 0.000 claims abstract description 15
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 21
- 239000000956 alloy Substances 0.000 claims description 12
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 12
- 238000005498 polishing Methods 0.000 claims description 11
- 238000004381 surface treatment Methods 0.000 claims description 9
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 8
- 239000004626 polylactic acid Substances 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 238000005452 bending Methods 0.000 claims description 3
- 239000003462 bioceramic Substances 0.000 claims description 3
- 238000005524 ceramic coating Methods 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 239000002861 polymer material Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 abstract description 5
- 238000001356 surgical procedure Methods 0.000 abstract description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 3
- 239000011733 molybdenum Substances 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000005266 casting Methods 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 210000000481 breast Anatomy 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910000882 Ca alloy Inorganic materials 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 238000001574 biopsy Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000003902 lesion Effects 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 208000026310 Breast neoplasm Diseases 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- XVYHFPMIBWTTLH-UHFFFAOYSA-N [Zn].[Mg].[Ca] Chemical compound [Zn].[Mg].[Ca] XVYHFPMIBWTTLH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000035807 sensation Effects 0.000 description 2
- 238000002560 therapeutic procedure Methods 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- -1 manganese, rare earth Chemical class 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002980 postoperative effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B90/00—Instruments, implements or accessories specially adapted for surgery or diagnosis and not covered by any of the groups A61B1/00 - A61B50/00, e.g. for luxation treatment or for protecting wound edges
- A61B90/39—Markers, e.g. radio-opaque or breast lesions markers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/04—X-ray contrast preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/22—Echographic preparations; Ultrasound imaging preparations ; Optoacoustic imaging preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B90/00—Instruments, implements or accessories specially adapted for surgery or diagnosis and not covered by any of the groups A61B1/00 - A61B50/00, e.g. for luxation treatment or for protecting wound edges
- A61B90/39—Markers, e.g. radio-opaque or breast lesions markers
- A61B2090/3904—Markers, e.g. radio-opaque or breast lesions markers specially adapted for marking specified tissue
- A61B2090/3908—Soft tissue, e.g. breast tissue
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B90/00—Instruments, implements or accessories specially adapted for surgery or diagnosis and not covered by any of the groups A61B1/00 - A61B50/00, e.g. for luxation treatment or for protecting wound edges
- A61B90/39—Markers, e.g. radio-opaque or breast lesions markers
- A61B2090/3966—Radiopaque markers visible in an X-ray image
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B90/00—Instruments, implements or accessories specially adapted for surgery or diagnosis and not covered by any of the groups A61B1/00 - A61B50/00, e.g. for luxation treatment or for protecting wound edges
- A61B90/39—Markers, e.g. radio-opaque or breast lesions markers
- A61B2090/3991—Markers, e.g. radio-opaque or breast lesions markers having specific anchoring means to fixate the marker to the tissue, e.g. hooks
Abstract
The present invention relates to one kind with locator markers and preparation method thereof made of degradable metal,The locator markers are made with pure magnesium or magnesium alloy,Wherein,Content of impurities is less than 0.01% mass fraction in pure magnesium and magnesium alloy,The locator markers are at least woven by three magnesium silks,And the positioning end for winding end with one and being connected to the winding end,The positioning end is claw-like or anchor-shaped structure,The tensile strength of the locator markers is more than 200 megapascal,Elongation after fracture is more than 10%,Internal degradation rate is less than 0.5mm/,The locator markers can develop under ultrasound and X-ray,Surgical procedure and aftertreatment process can pass through ultrasonic or molybdenum target X-ray detection to the position of marker,And with the progress of aftertreatment,Locator markers are gradually degraded,It is substantially absorbed into the surrounding tissues or is metabolized out human body,It is taken out without second operation.
Description
Technical field
The present invention relates to one kind be related to breast tissue in tumor of breast therapeutic process in preoperative biopsy, art excision and art
The locator markers treated afterwards, especially one kind is with locator markers and preparation method thereof made of degradable metal.
Background technology
Since lesion is small, clinic can not touch Minute breast lesion, in label, surgical procedure and postoperative after biopsy sampling
It is required to precise positioning in treatment, avoids operation from cutting off excessive normal structure, while ensuring the accuracy of diagnosing and treating.
Locator markers material used at present is generally titanium, titanium alloy or stainless steel material.For needing excision of performing the operation
Tumor of breast, marker can cut off taking-up together with lesion and part normal structure.And for aftertreatment or biopsy after
It is not required to the patient of operation, marker can be retained in vivo for a long time.Existing locator markers are usually with nondegradable metal material
It is made, it is thus possible to bring foreign body sensation to patient, it is also possible to be moved to other positions, or even second operation is needed to take out label
Object brings potential risks and hidden danger to patient.
Degradable pure magnesium and magnesium alloy biomaterials have good medical prospect, after being implanted into human body in surrounding tissue
The water gradually degradation that reacts form magnesium ion or other alloy ions, final metabolism excretes.It is suitable by selecting
Alloying element and control impurity content in metal, the degradation rate and biological safety of magnesium alloy can be controlled, avoid degrading
It is too fast that marker is caused to disappear or introduce in advance under image potential biological safety risk, marker can also be thrown
Light or surface prepares coating adjust the degradation rate of pure magnesium and magnesium alloy materials, improve biocompatibility, meet different treatment mesh
Demand.
Inventor by using degradable pure magnesium or magnesium alloy materials in view of this, be applied to locator markers, to solve
Defect existing for certainly existing locator markers.
Invention content
It is made, may be brought to patient of nondegradable metal or alloy material in order to solve existing locator markers
Foreign body sensation, it is also possible to be moved to other positions, or even second operation is needed to take out marker, potential risks are brought to patient
And hidden danger, the main purpose of the present invention is to provide one kind with locator markers and preparation method thereof made of degradable metal,
The locator markers are made with pure magnesium or magnesium alloy, wherein and content of impurities is less than 0.01% mass fraction in magnesium alloy,
The locator markers are at least knitted to form positioning end by three magnesium silks, which can be fixed on people with positioning end
Internal portion, and gradually degradation at any time, are substantially absorbed into the surrounding tissues or are metabolized out human body, taken out without second operation.
The present invention with technological means be to provide one kind with locator markers made of degradable metal, feature
It is, including：
One marker ontology, by the strip that at least three magnesium silks are entwined made by pure magnesium silk or magnesium alloy
Structure, one end of the marker ontology form the winding end wound each other, and the other end forms the positioning end detached each other, should
Positioning end is for being fixed on tissue.
It is preferred that the locator markers, used by pure magnesium silk or magnesium alloy content of impurities be less than
0.01% mass fraction.
Preferably, the locator markers, described in locator markers tensile strength be more than 200 megapascal, break
Elongation is more than 10% afterwards, and internal degradation rate is less than 0.5mm/.
Preferably, the positioning end of the locator markers, the marker ontology mutually uniformly divides in 120 degree of angles
Cloth, the positioning end are pre-bent into certain radian with the winding end touching position.
Preferably, the locator markers, the long axis of positioning end relative index's object ontology of the marker ontology
The anchor-shaped structure for the inverted V-shaped that about 135 degree~165 degree of outward bending.
Preferably it is the locator markers, which is characterized in that the length of the positioning end accounts for the marker ontology overall length
The one third of degree is to a quarter.
The present invention with technological means be to provide a kind of prepare with locator markers made of degradable metal
Preparation method includes following steps：
Magnesium silk forming step, material can be selected from pure magnesium or magnesium alloy materials, and content of impurities is less than 0.01% mass point
Number takes extruding, drawing or the deformation technique swaged to be processed into the silk material of diameter 0.5mm to 0.8mm；
Locator markers forming step, by previous step silk material formed thereby at least three one end coilings together at
One end for a locator markers, the locator markers forms a winding end, and certain angle is outwardly or inwardly bent in the other end
The positioning end of degree；
Surface treatment step, the locator markers can remove surface oxide layer by electrochemical polish, or on surface
Prepares coating reaches the degradation rate for adjusting magnesium alloy, improves the effect of biocompatibility.
Preferably, the preparation method of the locator markers, in surface treatment step using electrochemical polish into
Row processing, anode are the locator markers, and cathode is stainless steel electrode, after polished, the locator markers surface is made to form light
Bright mirror finish layer, is dried using washes of absolute alcohol.
Preferably, the preparation method of the locator markers uses the side of prepares coating in surface treatment step
When formula is surface-treated, coat type be degradable high polymer material or magnesia, magnesium hydroxide coating or avoid calcic,
The bio-ceramic coating of P elements.
Preferably it is the preparation method of the locator markers, a polylactic acid coating is prepared in surface treatment step,
By the locator markers in absolute ethyl alcohol and perchloric acid mixed polishing solution electrobrightening, dried in the air with washes of absolute alcohol after polishing
It is dry, the polylactic acid coating of about 10~30 microns of thickness is prepared on the locator markers surface using the method for spraying.
The present invention utilize provided with locator markers and preparation method thereof made of degradable metal, can obtain
Effect is promoted：
1, the locator markers are made with pure magnesium or magnesium alloy, can be developed under ultrasound and X-ray, surgical procedure and art
Therapeutic process can be by ultrasound or molybdenum target X-ray detection to the position of marker afterwards, and can remove table by electrochemical polish
Face oxide layer, or in surface prepares coating biocompatibility is improved to adjust the degradation rate of magnesium alloy.
2, locator markers can be firmly attached to positioning end in tissue, be not susceptible to shift, with subsequently controlling
The progress for the treatment of, locator markers are gradually degraded with the time, are substantially absorbed into the surrounding tissues or are metabolized out human body, taken without second operation
Go out, wherein the compressible deformation of positioning end of locator markers is simultaneously sprung back, and can form claw-like or anchor-shaped, can effectively be grabbed
It takes in tissue and not easily to fall off or displacement.
Description of the drawings
Fig. 1 is the outside drawing of the first preferred embodiment of the present invention.
Fig. 2 is the outside drawing of the second preferred embodiment of the present invention.
Fig. 3 is the flow chart of the locator markers preparation method of the present invention.
Specific implementation mode
In order to understand the technical characteristic and practical effect of the present invention in detail, and can come according to the content of specification real
It applies, further with preferred embodiment as shown in drawings, is described in detail as after, please refer in first preferred embodiment such as Fig. 1
Shown in locator markers made of degradable metal, include a marker ontology 10A.
The length of marker ontology 10A be 10~20mm, outer most edge 1~3mm of diameter, marker ontology 10A be by
The strip structure that at least three magnesium silks are entwined made by pure magnesium silk or magnesium alloy, it is preferred that by each magnesium silk
Diameter 0.5mm~0.8mm.
One end of marker ontology 10A forms winding the end 11A, winding end 11A wound each other and can be punctured with one
Push rod location contacts in needle cannula form the positioning end 12A detached each other in the other end of marker ontology 10A, and composition should
Each magnesium silk of positioning end 12A is mutually in about 120 degree of equally distributed claw-like structures of angle, positioning end 12A and winding end 11A
Touching position is pre-bent into certain radian.The length of positioning end 12A accounts for the one third of the marker ontology 10A total lengths
To a quarter, positioning end 12A is set to have enough length to be formed conducive to fixed shape, the locator markers are captured
Tensile strength be more than 200 megapascal, elongation after fracture be more than 10%, internal degradation rate be less than 0.5mm/.
The application method of first preferred embodiment of the invention is as follows, and marker ontology 10A is put into a puncture when use
In needle cannula, push a push rod of the puncture needle casing that can marker ontology 10A be launched in anchor point, the marker ontology
The positioning end 12A of 10A is pierced into breast tissue and fixation under thrust, since marker ontology 10A is pure magnesium silk or magnesium
Made by alloy, it can develop under ultrasound and X-ray, surgical procedure and aftertreatment process can pass through ultrasound or molybdenum target X-ray
Detect the position of marker ontology 10A.With the progress of aftertreatment, marker ontology 10A can gradually be dropped with the time
Solution, average internal degradation rate are less than 0.5 millimeter/year, it is preferred that average 0.15 millimeter/year~0.38 of internal degradation rate
Millimeter/year.
As shown in Fig. 2, it is roughly the same with first preferred embodiment embodiment, difference exists the second embodiment of the present invention
In one end of the positioning end 12B shapes of marker ontology 10B, marker ontology 10B is winding end 11B, the other end
For positioning end 12B, the length of positioning end 12B accounts for the one thirds of the marker ontology 10B total lengths to a quarter, and second
Preferred embodiment form about 135 degree of the long axis outward bending of each magnesium silk relative index object ontology 10B of positioning end 12B~
165 degree, and form the anchor-shaped structure of inverted V-shaped, wherein it is uniform in 120 degree of angles in space between each magnesium silk of positioning end 12B
Distribution, application method it is roughly the same with the first preferred embodiment, not in this to go forth.
Invention also provides a kind of locator markers as shown in Figure 3 preparing the first, second preferred embodiment of the invention
Preparation method, step includes magnesium silk forming S1, locator markers forming S2, surface treatment S3.
Magnesium silk forming step S1：Material can be selected from pure magnesium material, can be commercially available pure magnesium ingot casting, and content of magnesium is more than 99.99%
Mass fraction, other impurities composition such as iron, silicon, nickel, copper, aluminium, manganese, zinc impurity total content are less than 0.01% mass fraction, or can
The selection of material is for example pure magnesium zinc calcium alloy of magnesium alloy materials, wherein content of magnesium is more than 99% mass fraction, Zn content about 0.87%
Mass fraction, calcium content about 0.046%, other impurities such as aluminium, copper, iron, manganese, nickel, about 0.008% mass of silicon impurities total content point
Number, the pure magnesium material do not need solution heat treatment, the magnesium alloy materials need to after solution heat treatment, take extruding, drawing,
It swages and waits deformation techniques, obtain tensile strength and be more than the silk material of 200 megapascal, elongation after fracture more than 10%.The method of smelting
Including but not limited to atmosphere protection melting, vacuum melting.The selection of alloying element fully considers biological safety, in of the invention
Magnesium alloy materials are preferably magnesium-zinc alloy, magnesium calcium alloy, magnesium zinc calcium alloy, to avoid or the alloys such as control aluminium, zirconium, manganese, rare earth
Constituent content.
When material can be selected from pure magnesium material, used pure magnesium ingot casting is squeezed into diameter 1 after 250 degree of heat preservations in 3 hours
~2mm silk materials, extrusion ratio 16:1, extruding rate 0.5mm/s.By the silk material of extruding further across 16~40 passage hot pull works
Skill is processed into diameter 0.5mm silk materials.The tensile strength of this silk material can reach 220 megapascal, elongation after fracture 12%.
When material can be selected from magnesium alloy materials, used magnesium alloy ingot after 350 degree of solution heat treatment in 16 hours,
Diameter 12mm bars are squeezed into, 330 degree of temperature, extrusion ratio 17 are squeezed:1, extruding rate 0.33mm/s.The bar of extruding is through 22
Secondary swage obtains diameter 0.8mm silk materials.This 230 megapascal of silk material tensile strength, elongation after fracture 11.5%.
Locator markers shape S2：At least three one end is wound on using magnesium silk forming step S1 silk materials formed thereby
Become locator markers together, one end of locator markers forms winding end, certain angle is outwardly or inwardly bent in the other end
Degree, to form the positioning end of claw-like or anchor-shaped.
It is surface-treated S3：The locator markers can remove surface oxide layer by electrochemical polish, or in surface system
Standby coating improves biocompatibility to adjust the degradation rate of magnesium alloy.
Preferably, when the locator markers are handled its surface using the method for electrochemical polish, anode is
Locator markers, cathode are stainless steel electrode.0 degree, voltage 7V of polish temperature, the polishing fluid used are volume 8:1 anhydrous second
Alcohol and perchloric acid, additive are the glucose solution of the citric acid and 0.3g/L of 1.5g/L.After polishing in 30 seconds, make telltale mark
Object surface forms bright mirror finish layer.Locator markers after being dried using washes of absolute alcohol as implantation breast tissue
It uses.
When locator markers are surface-treated by the way of prepares coating, coat type is degradable macromolecule material
Material or magnesia, magnesium hydroxide coating, avoid the bio-ceramic coating of calcic, P elements, prevent group again after calcium, P elements degradation
Knit middle deposition.The preparation method of coating includes but not limited to self assembly, coating, alkali heat-treatment, chemical oxidation.
Preferably, a polylactic acid coating is prepared on locator markers surface, method is as follows, and locator markers are in anhydrous second
Electrobrightening 2min in alcohol and perchloric acid mixed polishing solution, 25 degree, voltage 10V of temperature are added with removing surface oxide layer and swaging
Work trace.It is dried with washes of absolute alcohol after polishing, thickness is then prepared on the locator markers surface using the method for spraying
About 10~30 microns of polylactic acid coating.
Use example difference with the preparation method of locator markers of the present invention is as follows：
With locator markers 10A as shown in Figure 1 is made, commercially available pure magnesium ingot casting, content of magnesium is used to be more than 99.99%
Mass fraction, iron, silicon, nickel, copper, aluminium, manganese, zinc impurity total content are less than 0.01% mass fraction.The ingot casting is small through 250 degree 3
Diameter 1~2mm silk materials, extrusion ratio 16 are squeezed into after Shi Baowen:1, extruding rate 0.5mm/s further pass through the silk material of extruding
It crosses 16~40 passage hot-pull techniques and is processed into diameter 0.5mm silk materials, this 220 megapascal of silk material tensile strength, elongation after fracture
12%.
By above-mentioned Wire-winding at locator markers 10A shown in FIG. 1 after, using the method for electrochemical polish to its surface
It is handled：Anode is marker, and cathode is stainless steel electrode.0 degree, voltage 7V of polish temperature, the polishing fluid used are volume
8:1 absolute ethyl alcohol and perchloric acid, additive are the glucose solution of the citric acid and 0.3g/L of 1.5g/L.It was polished through 30 seconds
Afterwards, marker surface forms bright mirror finish layer.Mark after being dried using washes of absolute alcohol as implantation breast tissue
Remember that object uses.
With locator markers 10B as shown in Figure 2 is made, raw material are pure magnesium ingot casting, zinc granule, calcium block, using true
Empty melting obtains 0.87% mass fraction of Zn content, and 0.046% mass fraction of calcium content, aluminium, copper, iron, manganese, nickel, silicon impurities are total
0.0080% mass fraction of content.The ingot casting is squeezed into diameter 12mm bars after 350 degree of solution heat treatment in 16 hours, squeezes
Press 330 degree of temperature, extrusion ratio 17:1, extruding rate 0.33mm/s.The bar of extruding swages through 22 passages and obtains diameter 0.8mm
Material.This 230 megapascal of silk material tensile strength, elongation after fracture 11.5%.
By above-mentioned Wire-winding at locator markers 10B shown in Fig. 2 after, polylactic acid coating is prepared on its surface, makes this
Locator markers 10B electrobrightening 2min in absolute ethyl alcohol and perchloric acid mixed polishing solution, 25 degree, voltage 10V of temperature, to go
Except surface oxide layer and cutter trade of swaging.It is dried with washes of absolute alcohol after polishing, is then being marked using the method for spraying
Object surface prepares the polylactic acid coating of about 10~30 microns of thickness.
The above is only the preferred embodiment of the present invention, is not intended to limit the present invention in any form, Ren Hesuo
Belong to technical field those of ordinary skill, if in the range of not departing from carried technical characteristic of the invention, utilization is disclosed
The equivalent embodiment for locally changing or modifying made by technology contents, in the range of still falling within the technology of the present invention feature.
Claims (10)
1. one kind is with locator markers made of degradable metal, which is characterized in that including：
One marker ontology, by the strip knot that at least three magnesium silks are entwined made by pure magnesium silk or magnesium alloy
Structure, one end of the marker ontology form the winding end wound each other, and the other end forms the positioning end detached each other, this is fixed
Position end is for being fixed on tissue.
2. locator markers according to claim 1, which is characterized in that impurity is total in used pure magnesium silk or magnesium alloy
Content is less than 0.01% mass fraction.
3. locator markers according to claim 2, which is characterized in that the tensile strength of the locator markers is more than
200 megapascal, elongation after fracture are more than 10%, and internal degradation rate is less than 0.5mm/.
4. locator markers according to claim 1, which is characterized in that the positioning end of the marker ontology is mutually in maximum
120 degree of angles are uniformly distributed, which is pre-bent into certain radian with the winding end touching position.
5. locator markers according to claim 1, which is characterized in that positioning end relative index's object of the marker ontology
The anchor-shaped structure of the inverted V-shaped of about 135 degree~165 degree of the long axis outward bending of ontology.
6. locator markers according to any one of claim 1 to 5, which is characterized in that the length of the positioning end accounts for this
The one third of marker ontology total length is to a quarter.
7. a kind of preparation method preparing locator markers described in claim 1, which is characterized in that include the following steps：
Magnesium silk forming step, material can be selected from pure magnesium or magnesium alloy materials, and content of impurities is less than 0.01% mass fraction, adopts
Extruding, drawing or the deformation technique swaged is taken to be processed into the silk material of diameter 0.5mm to 0.8mm；
Previous step silk material formed thereby is become one by locator markers forming step together at least three one end coilings
One end of locator markers, the locator markers forms a winding end, is outwardly or inwardly angled in the other end
Positioning end；
Surface treatment step, the locator markers can remove surface oxide layer by electrochemical polish, or be prepared on surface
Coating reaches the degradation rate for adjusting magnesium alloy, improves the effect of biocompatibility.
8. the preparation method of locator markers according to claim 7, which is characterized in that used in surface treatment step
Electrochemical polish is handled, and anode is the locator markers, and cathode is stainless steel electrode, after polished, makes the telltale mark
Object surface forms bright mirror finish layer, is dried using washes of absolute alcohol.
9. the preparation method of locator markers according to claim 7, which is characterized in that used in surface treatment step
When the mode of prepares coating is surface-treated, coat type be degradable high polymer material or magnesia, magnesium hydroxide coating,
Or avoid the bio-ceramic coating of calcic, P elements.
10. the preparation method of locator markers according to claim 7, which is characterized in that made in surface treatment step
A standby polylactic acid coating, by the locator markers in absolute ethyl alcohol and perchloric acid mixed polishing solution electrobrightening, used after polishing
Washes of absolute alcohol dries, and the polylactic acid of about 10~30 microns of thickness is prepared on the locator markers surface using the method for spraying
Coating.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109330674A (en) * | 2018-09-07 | 2019-02-15 | 西安卓恰医疗器械有限公司 | A kind of internal fixation system and its usage mode |
| CN111214284A (en) * | 2020-01-21 | 2020-06-02 | 沪创医疗科技（上海）有限公司 | Degradable metal cable internal fixing system and application |
| CN111481272A (en) * | 2020-05-14 | 2020-08-04 | 北京大学第三医院（北京大学第三临床医学院） | Ultrasonic guided puncture positioning guide line and manufacturing method thereof |
| WO2020154935A1 (en) * | 2019-01-30 | 2020-08-06 | 唐山哈船科技有限公司 | Device for locating tumour after surgery |
| CN112274263A (en) * | 2020-11-05 | 2021-01-29 | 汤小江 | Bioabsorbable mammary tissue positioning mark clamp and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101385875A (en) * | 2007-09-12 | 2009-03-18 | 中国科学院金属研究所 | Complete degradable absorbent medicine slow-release magnesium alloy bracket and use thereof |
| CN102908216A (en) * | 2012-10-30 | 2013-02-06 | 东南大学 | Biodegradable medical human body cavity channel inner bracket and preparation method thereof |
| CN103083732A (en) * | 2011-10-28 | 2013-05-08 | 宛新建 | Biodegradable magnesium alloy braided scaffold for resisting benign and malignant biliary stricture and preparation method thereof |
| CN103876841A (en) * | 2014-03-25 | 2014-06-25 | 金龙 | Marker, manufacturing method of marker and positioning system manufactured with marker |
| CN106361476A (en) * | 2016-09-13 | 2017-02-01 | 郑州大学 | Woven fully-degradable magnesium alloy airway stent and preparation method thereof |
| CN208851651U (en) * | 2018-04-11 | 2019-05-14 | 西安卓恰医疗器械有限公司 | With locator markers made of degradable metal |
-
2018
- 2018-04-11 CN CN201810324357.3A patent/CN108378929A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101385875A (en) * | 2007-09-12 | 2009-03-18 | 中国科学院金属研究所 | Complete degradable absorbent medicine slow-release magnesium alloy bracket and use thereof |
| CN103083732A (en) * | 2011-10-28 | 2013-05-08 | 宛新建 | Biodegradable magnesium alloy braided scaffold for resisting benign and malignant biliary stricture and preparation method thereof |
| CN102908216A (en) * | 2012-10-30 | 2013-02-06 | 东南大学 | Biodegradable medical human body cavity channel inner bracket and preparation method thereof |
| CN103876841A (en) * | 2014-03-25 | 2014-06-25 | 金龙 | Marker, manufacturing method of marker and positioning system manufactured with marker |
| CN106361476A (en) * | 2016-09-13 | 2017-02-01 | 郑州大学 | Woven fully-degradable magnesium alloy airway stent and preparation method thereof |
| CN208851651U (en) * | 2018-04-11 | 2019-05-14 | 西安卓恰医疗器械有限公司 | With locator markers made of degradable metal |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109330674A (en) * | 2018-09-07 | 2019-02-15 | 西安卓恰医疗器械有限公司 | A kind of internal fixation system and its usage mode |
| WO2020154935A1 (en) * | 2019-01-30 | 2020-08-06 | 唐山哈船科技有限公司 | Device for locating tumour after surgery |
| CN111214284A (en) * | 2020-01-21 | 2020-06-02 | 沪创医疗科技（上海）有限公司 | Degradable metal cable internal fixing system and application |
| CN111214284B (en) * | 2020-01-21 | 2022-07-05 | 沪创医疗科技（上海）有限公司 | Degradable metal cable internal fixing system and application |
| CN111481272A (en) * | 2020-05-14 | 2020-08-04 | 北京大学第三医院（北京大学第三临床医学院） | Ultrasonic guided puncture positioning guide line and manufacturing method thereof |
| CN111481272B (en) * | 2020-05-14 | 2022-04-12 | 北京大学第三医院（北京大学第三临床医学院） | Ultrasonic guided puncture positioning guide line and manufacturing method thereof |
| CN112274263A (en) * | 2020-11-05 | 2021-01-29 | 汤小江 | Bioabsorbable mammary tissue positioning mark clamp and preparation method thereof |
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