CN103233143B - A kind of cobalt-based porcelain alloy and application thereof - Google Patents
A kind of cobalt-based porcelain alloy and application thereof Download PDFInfo
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 64
- 239000010941 cobalt Substances 0.000 title claims abstract description 64
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 64
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000010949 copper Substances 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
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- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 15
- 239000011572 manganese Substances 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
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- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 9
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010937 tungsten Substances 0.000 claims abstract description 8
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- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000007669 thermal treatment Methods 0.000 claims abstract description 5
- 239000011651 chromium Substances 0.000 claims description 21
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 17
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 14
- 239000011733 molybdenum Substances 0.000 claims description 13
- 238000009413 insulation Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
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- 239000005548 dental material Substances 0.000 claims description 6
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Abstract
The invention provides a kind of novel cobalt-based porcelain alloy, its chemical composition is by weight: C≤0.08%, Cr:16 ~ 24%, Fe:10 ~ 20%, Mn:5 ~ 15%, Mo:2 ~ 8%, W:2 ~ 8%, Cu:1 ~ 3%, N≤0.4%, Ni≤0.1%, S < 0.01%, P < 0.02%, Co surplus.The present invention replaces the expensive cobalt element of part by adding the elements such as iron, manganese and tungsten, the thermal expansivity of porcelain alloy is adjusted by W content, porcelain alloy is made to have excellent golden porcelain bonding force, mechanical property and the corrosion resisting property of porcelain alloy is optimized further by nitrogen element, make copper disperse educt by special thermal treatment simultaneously thus make alloy have certain antibacterial, therefore this alloy has great advantage as dental alloy.Porcelain alloy of the present invention also can be used on the aspects such as surgical implant, medicine equipment, food food and drink apparatus, jewellery.
Description
Technical field
The present invention relates to cochrome, specifically to come of age the denture prosthesis cochromes such as bridge for porcelain corona.
Background technology
Odontopathy morbidity is all very high in countries in the world, and with regard to China, dental patient reaches 800,000,000 more than.And defect of teeth, denture lack that to split with dentition defect be common disease in odontopathy, artificial tooth is usually adopted to repair.The good mechanical performance such as alloy material intensity, hardness, wear resistance, weather resistance and toughness, after particularly lost wax process technology introduces dental field, alloy becomes main repair materials.At present due to potential sensitization and the harm such as carcinogenic of nickel in ni-cr porcelain alloy, cause ni-cr porcelain alloy gradually substitute by cobalt chromium porcelain alloy.
Cobalt chromium porcelain alloy is applied to the earliest transplants medical treatment, and be used as the use of hip joint, due to its corrosion resistance nature, comparatively nickel-base alloy is good, and golden porcelain combines good, has become the main porcelain alloy of dentures repai.Cobalt base alloy take cobalt as matrix, add the alloy material that the elements such as chromium, nickel, molybdenum and tungsten are formed, cobalt base alloy is its Typical Representative with vitallium, Medical Cobalt-Based Alloys has good corrosion resistance nature, abrasion resistance properties and thermal fatigue resistance, thermal conductivity is high, thermal expansivity is lower, and Young's modulus does not change with its Strength Changes.
Dental material belongs to biomaterial, and except requiring that alloy has high intensity, hardness and ductility, fusing point is low, good fluidity, shrinkage coefficient are little; Also require that excellent, the suitable thermal expansivity of alloy chromaticness has good mating with porcelain powder; The free-running property required and the shrinkage coefficient (namely solidifying and the contraction in process of cooling) be suitable for mutually with the embedded material coefficient of expansion; Also require that the structure stability of alloy is good, owing to using in the oral cavity for a long time, require that alloy has good biocompatibility, anti-oxidant and wear-corrosion resistance.
Summary of the invention
The object of the present invention is to provide a kind of cobalt-based porcelain alloy, consider that cobalt is a kind of grand strategy resource, most countries lacks cobalt in the world, the problem such as expensive of cobalt, the present invention is on vitallium basis, reduce the content of cobalt and chromium, add ferro element and manganese element in right amount, and add nitrogen unit usually optimized force performance and corrosion resisting property.Consider that oral environment bacteria's numbers and species is numerous and diverse simultaneously, add amount of copper element.Cobalt-based porcelain alloy of the present invention has excellent antibacterial and golden porcelain binding ability, there is excellent mechanical property and corrosion resisting property simultaneously, not containing the nickel element of the harm such as potential sensitization, and low cost, significant to dentures repai, there is important society and economic implications.
Based on above object, the invention provides a kind of cobalt-based porcelain alloy, it is characterized in that: its chemical composition is by weight: carbon C≤0.08%, chromium Cr:16 ~ 24%, iron Fe:10 ~ 20%, manganese Mn:5 ~ 15%, molybdenum Mo:2 ~ 8%, tungsten W:2 ~ 8%, copper Cu:1 ~ 3%, nitrogen N≤0.4%, nickel≤0.1%, sulphur S < 0.01%, phosphorus P < 0.02%, cobalt Co: surplus.Be preferably: carbon C≤0.08%, chromium Cr:20 ~ 24%, iron Fe:16-18%, manganese Mn:8-12%, molybdenum Mo:4 ~ 6%, tungsten W:2 ~ 4%, copper Cu:1 ~ 3%, nitrogen N:0.2 ~ 0.4%, nickel≤0.1%, sulphur S < 0.01%, phosphorus P < 0.02%, cobalt Co: surplus.
In cobalt-based porcelain alloy provided by the present invention, in order to avoid potential sensitization and the harm such as carcinogenic of nickel element, consider the residual content of nickel in metallurgical raw material, in cobalt base alloy of the present invention, control nickel≤0.1 (wt%).
Cobalt-based porcelain alloy provided by the present invention, in order to ensure excellent mechanical property and corrosion resisting property, avoid carbide too much in alloy to be formed, in cobalt-based porcelain alloy of the present invention, carbon content preferably controls at C≤0.08 (wt%)
Cobalt-based porcelain alloy provided by the present invention contains nitrogen element, first nitrogen contributes to putting forward heavy alloyed intensity and erosion resistance, according to spot corrosion and crevice corrosion drag approximate formula PREN=%Cr+3.3%Mo+ (13-30) %N, can find out that nitrogen and chromium, molybdenum acting in conjunction are 20 ~ 30 times of chromium independent role effect.Secondly the nitrogen element in alloy is macroelement in human body, is safe from harm to human body.Therefore consider the impact of metallurgy factor, in cobalt-based porcelain alloy of the present invention, Control of Nitrogen Content is at N≤0.4%.
Cobalt-based porcelain alloy provided by the present invention contains chromium element, and chromium improves the topmost alloying element of cobalt base alloy solidity to corrosion, and in oxidizing medium, chromium can make alloy surface to generate rapidly chromic oxide (such as Cr
2o
3) passive film, this layer of passive film is very fine and close and stable, even if once destroyed also to recover rapidly.Chromium effectively improves the pitting resistance of cobalt base alloy simultaneously, and when having molybdenum and nitrogen to exist in alloy simultaneously, this validity of chromium is strengthened greatly.Due to the anti-corrosion element that chromium is main in stainless steel, and improve the solubleness of nitrogen in alloy, therefore in cobalt-based porcelain alloy of the present invention, chromium content controls 16 ~ 24%.
Cobalt-based porcelain alloy provided by the present invention contains ferro element, and first iron is a kind of trace element of needed by human, participates in the most of metabolism of human body.Secondly in cobalt-based porcelain alloy of the present invention, adding of ferro element is mainly used for the expensive cobalt element of part in alternative alloy, to reach the object reduced costs.Iron can form continuous print sosoloid with cobalt in the alloy, does not affect the performance of cobalt base alloy, and in cobalt-based porcelain alloy of the present invention, iron level controls 10 ~ 20%.
Cobalt-based porcelain alloy provided by the present invention contains molybdenum element, and first molybdenum is a kind of important micro elements needed by human.Secondly molybdenum adds in cobalt base alloy and is mainly used to put forward the heavy alloyed solidity to corrosion particularly performance such as resistance to spot corrosion and crevice corrosion.Research Literature shows that the resistance to spot corrosion of molybdenum and the ability of crevice corrosion are about 3 times of chromium, and great many of experiments is pointed out, molybdenum mainly strengthens the anti-corrosion effect of chromium in steel.Therefore in cobalt-based porcelain alloy of the present invention, molybdenum content controls 2 ~ 8%.
Cobalt-based porcelain alloy provided by the present invention contains manganese element, and first manganese is the trace element of needed by human, and manganese all has important effect in animals and plants and human body, it is the cofactor of enzyme, can promote that VITAMIN is synthesized, manganese participates in the anabolism of protein, can also activate archaeal dna polymerase etc.Secondly the manganese element in alloy is austenite former, has the effect of strongly stablizing cobalt base alloy austenitic matrix.In alloy of the present invention, the most important effect of manganese element is the solubleness increasing nitrogen in alloy, and the content of nitrogen in adjustment alloy, consider the nitrogen content in alloy, therefore in cobalt-based porcelain alloy of the present invention, Fe content controls 5 ~ 15%.
Cobalt-based porcelain alloy provided by the present invention contains W elements, tungsten add mainly in order to adjust because iron and manganese element add the alloy density caused, the change of the physical quantity such as Young's modulus and thermal expansivity, because the density relationship of thermal expansivity and material is close, therefore the tungsten by adding different content adjusts the thermal expansivity of cobalt-based porcelain alloy of the present invention, makes it have excellent golden porcelain bonding force.Therefore in cobalt-based porcelain alloy of the present invention, W content controls 2 ~ 8%.
Cobalt-based porcelain alloy provided by the present invention contains copper, and adding of copper can fall low-alloyed fusing point on the one hand, strengthens mobility.Copper is the prerequisite that cobalt-based porcelain alloy of the present invention has antibacterial on the other hand, the solubleness of copper in cobalt declines gradually along with temperature reduces, therefore porcelain alloy of the present invention can by special antibacterial heat-treatment (thermal treatment process be: 400-500 DEG C of insulation 0.5-5h), part copper-rich phase even dispersion can be separated out in alloy substrate, thus give cobalt chromium porcelain alloy broad-spectrum antimicrobial function.Consider the hot workability of too much copper content influence alloy, therefore in cobalt-based porcelain alloy of the present invention copper content control 1 ~ 3%.
In cobalt-based porcelain alloy provided by the present invention, sulphur and phosphorus are regarded as detrimental impurity, owing to needing to adjust nitrogen content by adjustment Fe content in cobalt-based porcelain alloy of the present invention, in order to avoid the formation of manganese sulfide impurity, control sulphur content in cobalt base alloy of the present invention and lower than 0.01%, phosphorus content should be controlled below 0.02%.
Present invention also offers the antibacterial heat-treatment technique of above-mentioned cobalt chromium porcelain alloy, concrete technology is: at 1150 DEG C-1200 DEG C insulation 0.5-2h, the copper in alloy is made to be solid-solution in matrix sufficiently uniformly, after water-cooled to room temperature, according to the copper content height in alloy, at 400 DEG C-500 DEG C insulation 0.5-5h, make part copper from alloy, separate out the copper-rich phase of q.s, ensure certain antibacterial ability.
The advantage of cobalt-based porcelain alloy provided by the present invention:
First contrast the cobalt chrome molybdenum porcelain alloy of clinical application, in alloy, with the addition of copper, after special thermal treatment, make alloy have certain anti-microbial property, use in oral environment and contribute to alleviating the oral diseases such as various focusing depths represented.
Secondly replacing the expensive cobalt element of part by adding iron, manganese and nitrogen element, significantly reducing the preparation cost of cobalt base alloy.Iron and manganese element are all the trace elements of needed by human, do not have serious harm to human body.The nitrogen element added in alloy is effective austenite stable element, can effectively put forward heavy alloyed mechanical property and corrosion resisting property simultaneously.
3rd, the thermal expansivity of porcelain alloy is adjusted by W elements content wherein, according to different porcelain powder, can adjust alloying constituent, obtains the porcelain alloy with the perfect cooperation of porcelain powder thermal expansivity, finally has excellent golden porcelain bonding force.
4th, porcelain alloy has excellent plasticity and toughness, and being hopeful to change traditional casting and molding method is pressure forming.
Range of application:
Cobalt-based porcelain alloy of the present invention, relative to traditional cobalt base alloy, there is certain antibacterial and excellent mechanics and corrosion resisting property, and cost is low, as porcelain alloy, there is great advantage, can be used as dental material and be widely used in dentures repai material and dummy, as made various tooth inlay, 3/4 hat, complete crown, veneer hat, short span bridge and Long Span Bridge etc., also can be applicable to the field such as the Srgery grafting fields such as orthopaedics and food food and drink apparatus, clock and watch, jewellery.
Embodiment
Dental cochrome of the present invention adopts conventional vacuum induction furnace to smelt, be cast into the bar of suitable dimension, the related physical performance of gained dentistry cochrome as cast condition bar and mechanical property: fusing point=1400-1550, thermal expansivity=13.8-14.9 × 10-6, σ b >=880MPa, σ 0.2 >=500MPa, δ 5 >=8%, Ψ >=5%, Hv5 >=260, the bonding force between alloy and porcelain can up to more than 300Mpa.
Embodiment:
Chemical composition ranges set by the present invention, in 25 kg capacity vacuum induction furnaces, smelted 4 stove steel and each 10 kilograms of 1 stove comparative alloy, its specific chemical composition is as shown in table 1.Alloy steel ingot of the present invention, at 1150 DEG C-1200 DEG C insulation 2h, is forged into 30mm heavy-gauge sheeting, then makes the copper in alloy be solid-solution in matrix sufficiently uniformly at 1150 DEG C of insulation 2h, after water-cooled to room temperature, makes the copper in steel be in hypersaturated state.Alloy 1 is at 400 DEG C of insulation 5h, and alloy 2 and 3 is respectively at 500 DEG C of insulation 3h and 2h, and preferred component alloy 4 is at 450 DEG C of insulation 3h, and the mechanical property recorded is as shown in table 2.
From embodiment test result, cobalt-based porcelain alloy of the present invention is by adding the cobalt-base alloy of iron and manganese alloy replacement costliness, and reduce carbon content by improving nitrogen content, compare the porcelain vitallium (comparative alloy) of Clinical practice, not only ensure higher intensity, significantly improve the plasticity and toughness of alloy simultaneously, show obvious cost performance.Preferred alloy semi-finals degree performance is closest to contrast porcelain alloy, but plasticity and toughness are better, and be conducive to the shaping of alloy, changing traditional casting is viscous deformation pressure forming.
The chemical composition of table 1 cochrome of the present invention
| Alloy | C | Cr | Mn | N | Mo | Fe | Ni | Cu | W | Co |
| Comparative alloy | 0.210 | 28.20 | 0.40 | 0.13 | 5.90 | 0.50 | 0.60 | -- | -- | Surplus |
| 1 | 0.036 | 19.6 | 6.5 | 0.15 | 3.14 | 18.3 | 0.01 | 1.36 | 2.8 | Surplus |
| 2 | 0.039 | 17.5 | 10.58 | 0.22 | 4.98 | 14.5 | 0.01 | 2.02 | 3.4 | Surplus |
| 3 | 0.044 | 22.8 | 14.77 | 0.37 | 2.35 | 11.9 | 0.02 | 2.65 | 4.8 | Surplus |
| 4 | 0.056 | 21.4 | 10.3 | 0.39 | 4.21 | 16.8 | 0.04 | 1.81 | 3.8 | Surplus |
The mechanical property of table 2 cochrome of the present invention
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to spirit of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (7)
1. a cobalt-based porcelain alloy, is characterized in that: its chemical composition is by weight: carbon C≤0.08%, chromium Cr:16 ~ 24%, iron Fe:10 ~ 20%, manganese Mn:5 ~ 15%, molybdenum Mo:2 ~ 8%, tungsten W:2 ~ 8%, copper Cu:1 ~ 3%, nitrogen N0.15 ~ 0.4%, nickel≤0.1%, sulphur S < 0.01%, phosphorus P < 0.02%, cobalt Co: surplus; Carry out antibacterial heat-treatment to cobalt-based porcelain alloy, thermal treatment process is: 400-500 DEG C of insulation 0.5-5h hour, makes part copper disperse educt in alloy.
2. according to cobalt-based porcelain alloy described in claim 1, it is characterized in that: carbon C≤0.08%, chromium Cr:20 ~ 24%, iron Fe:16-18%, manganese Mn:8-12%, molybdenum Mo:4 ~ 6%, tungsten W:2 ~ 4%, copper Cu:1 ~ 3%, nitrogen N:0.2 ~ 0.4%, nickel≤0.1%, sulphur S < 0.01%, phosphorus P < 0.02%, cobalt Co: surplus.
3. the heat treating method of a cobalt-based porcelain alloy as claimed in claim 1, it is characterized in that, concrete thermal treatment process is: at 1150 DEG C-1200 DEG C insulation 0.5-2h, the copper in alloy is made to be solid-solution in matrix sufficiently uniformly, after water-cooled to room temperature, according to the copper content height in alloy, at 400 DEG C-500 DEG C insulation 0.5-5h, make part copper from alloy, separate out the copper-rich phase of q.s.
4. one kind as claimed in claim 1 cobalt-based porcelain alloy as the application of dental material.
5., it is characterized in that as the application of dental material according to cobalt-based porcelain alloy described in claim 4: described dental material is dentures repai material or denture prosthesis.
6., it is characterized in that as the application of dental material according to cobalt-based porcelain alloy described in claim 5: this alloy is for making various tooth inlay, 3/4 hat, complete crown, veneer hat, short span bridge or Long Span Bridge.
7. one kind as claimed in claim 1 cobalt-based porcelain alloy in the application of Srgery grafting, food food and drink apparatus, clock and watch and field of jewelry.
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| CN104651669A (en) * | 2013-11-15 | 2015-05-27 | 中国科学院金属研究所 | Cast cobalt-based alloy used for antibacterial infection and heat treatment technology thereof |
| CN104831126A (en) * | 2015-05-14 | 2015-08-12 | 中国科学院金属研究所 | Antimicrobial cobalt-base material for dental corona products and heat treatment method thereof |
| CN105256173A (en) * | 2015-10-15 | 2016-01-20 | 谭华 | Preparation method for false tooth alloy material |
| CN105832563A (en) * | 2016-05-05 | 2016-08-10 | 东莞市爱嘉义齿有限公司 | 3D printing false tooth material |
| CN105861883B (en) * | 2016-05-10 | 2018-01-19 | 上海大学兴化特种不锈钢研究院 | A kind of high-ductility antibacterial medical Co-base alloy material |
| CN107365925B (en) * | 2017-06-26 | 2019-12-24 | 深圳市翔通光电技术有限公司 | Nitrogen-doped cobalt-chromium alloy and preparation method and application thereof |
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