CN102330022A - Novel martensite antimicrobial stainless steel, thermal processing method and application thereof - Google Patents
Novel martensite antimicrobial stainless steel, thermal processing method and application thereof Download PDFInfo
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Abstract
The invention provides novel martensite antimicrobial stainless steel, a thermal processing method and application thereof. The novel martensite antimicrobial stainless steel comprises the following chemical components in percent by weight: 0.16-0.25 percent of C, 0-1.00 percent of Si, 0-1.00 percent of Mn, 0-0.035 percent of P, 0-0.030 percent of S, 12.0-14.0 percent of Cr, 2.0-4.0 percent of Cu, 0.5-1.0 percent of Mo and the balance of Fe. The thermal treatment method comprises the following steps of: carrying out solid solution treatment at a temperature of 1000-1100 DEG C for 0.5-1h, oil-cooling to room temperature; preserving the temperature for 2-6h at a temperature of 500-800 DEG C, air-cooling to room temperature; carrying out solid solution for 3-10min at a temperature of 980-1020 DEG C, oil-cooling to room temperature; and preserving the temperature for 1-2h at a temperature of 150-250 DEG C, and air-cooling to room temperature. The novel martensite antimicrobial stainless steel can be widely applied to fields of sanitary ware, food utensils, tableware, cutters, medical apparatuses and instruments, and the like, and has a special broad-spectrum anti-bacterial property and more excellent corrosion resistance.
Description
Technical field
The invention belongs to the martensite stainless steel material field, be specifically related to a kind of novel martensite antimicrobial stainless steel and heat treating method and application.
Background technology
Stainless invention is a significant achievement on world's history of metallurgy, and stainless production has been established important material technological foundation for industrial and scientific-technical progress.Stainless steel has obtained widespread use in food, food and drink, health, communal facility, industry and people's daily life.Along with the continuous generation of public health events such as SARS, bird flu, people are increasingly high to the cleaning and the hygienic requirements of living environment and household utensils.People hope Stainless Steel Ware except having characteristics stainless and attractive in appearance, also will have other function such as anti-go mouldy, antibiotic.So, intersecting as Materials science and environmental science and develop a kind of type material of, anti-bacteria stainless steel arises at the historic moment.
Anti-bacteria stainless steel has the dual characteristics of structure and antibacterial concurrently; Not only have nontoxic, broad-spectrum antimicrobial, antibiotic timeliness long, do not produce characteristics such as resistance; And also be that other type anti-biotic material is incomparable at aspects such as goods are wear-resisting, attractive in appearance; The every nook and cranny that the research and development of anti-biotic material will make the human immune system expand human living space to all has very important realistic meaning and economic worth to improving people's living standard and social development.
An amount of copper (Cu) that adds is the important technology approach that develops the anti-bacteria stainless steel novel material in stainless steel, in disclosed cupric anti-bacteria stainless steel, mainly contains the cupric anti-bacteria stainless steel of austenite, ferritic, martensite three major types type.These anti-bacteria stainless steels all are basically on the composition basis of the common stainless steel of original correspondence; Through adding amount of copper element and special thermal treatment; And give stainless steel strong and broad-spectrum sterilization function; To the killing rate of common bacterias such as intestinal bacteria, streptococcus aureus all more than 99%, for example 304 types (austenite), 430 types (ferritic), 420 class cupric anti-bacteria stainless steels such as (martensites).
Martensite Stainless Steel is used widely in fields such as sanitary apparatus, food utensil, tableware, cutlery and medicine equipments with its high firmness characteristic; The 420 class Martensite Stainless Steel is its typical case representative, and the exploitation with cupric Martensite Stainless Steel of antibacterial will certainly bring new attraction with using.It is poor relatively than other type stainless steel that yet the main deficiency of Martensite Stainless Steel is exactly its solidity to corrosion, restricted its product development and application.
Molybdenum (Mo) is an alloy element commonly used in the steel, and it removes the carbide that has the hardening capacity that improves steel and under middle temperature, can form the Mo that disperse distributes (like Mo
2C) strengthen outside the matrix effect of steel, in austenitic stainless steel, also be used to further improve corrosion resisting property, especially pitting resistance.As in the 316 type austenitic stainless steels owing to add the Mo element of 2-3%, and its anti-spot corrosion (particularly chloride ion corrosion) performance is significantly improved.
Summary of the invention
In Martensite Stainless Steel, add to the invention property Cu and Mo element simultaneously; A kind of novel martensite antimicrobial stainless steel with broad-spectrum antimicrobial function and excellent anticorrosive performance is provided; And provide its heat treating method to reach in Application in Manufacturing Industry, to promote using more widely of martensite antimicrobial stainless steel.
For realizing above-mentioned purpose, technical scheme of the present invention is:
A kind of novel martensite antimicrobial stainless steel is characterized in that: by weight percentage, this stainless chemical ingredients is following: C:0.16-0.25; Si:0-1.00%; Mn:0-1.00%; P:0-0.035%; S:0-0.030%; Cr:12.0-14.0%; Cu:2.0-4.0%; Mo:0.5-1.0%; Surplus is Fe.
Further, Cu:3.0-3.5%; Mo:0.5-0.6%.
The Cu element is the important alloying element in this stainless steel, is to guarantee that stainless steel possesses the prerequisite of antibacterial.Cu content in the stainless steel of the present invention is 2.0-4.0 (wt) %, guaranteeing under the special thermal treatment condition, in steel, separating out copper-rich phase, thereby has good antimicrobial property.
The Cr element is a fixed alloying element in the Martensite Stainless Steel, and its effect is to form dense oxidation film and give stainless steel certain corrosion-resistant effect at stainless steel surface.
The C element is the reinforced alloys element in the Martensite Stainless Steel, and it is the strengthening element of martensitic stucture in the stainless steel, makes Martensite Stainless Steel keep higher hardness.
The effect of Mo element is the corrosion resisting property that under solid solution condition, further improves Martensite Stainless Steel.
The smelting and the working method of novel martensite antimicrobial stainless steel of the present invention and existing Martensite Stainless Steel are basic identical, but its special thermal treatment method is arranged, and comprise the steps:
(1) 1000-1100 ℃ solution treatment 0.5-1 hour, fully solid solution is in matrix to make copper in the steel, oil cooling makes the copper in the steel be in hypersaturated state to room temperature;
(2) 500-800 ℃ of insulation 2-6 hour, oversaturated copper is separated out from steel, form the copper-rich phase of q.s, air cooling is to room temperature;
(3) 980-1020 ℃ solution treatment 3-10 minute, oil cooling is to room temperature, when making martensite antimicrobial stainless steel keep the higher hardness of quenching attitude, controls the dissolving of rich copper precipitated phase, and makes the abundant solid solution of Mo in matrix;
(4) 150-250 ℃ is incubated 1-2 hour, the internal stress that forms when quenching to eliminate, and air cooling is to room temperature.
The application of the novel martensite antimicrobial stainless steel among the present invention can be widely used in fields such as sanitary apparatus, food utensil, tableware, cutlery and medicine equipment.
The invention has the beneficial effects as follows:
(1) added copper in the Martensite Stainless Steel of the present invention,, in stainless steel base, be distributed with rich copper precipitated phase, thereby given Martensite Stainless Steel excellent antimicrobial characteristic through after the special thermal treatment.
(2) the present invention makes the corrosion resisting property of Martensite Stainless Steel excellent more through in Martensite Stainless Steel, adding a certain amount of Mo element.
(3) the novel martensite antimicrobial stainless steel that is added with copper and molybdenum element of the present invention has improved stainless steel character, has enriched the material product kind of martensite antimicrobial stainless steel, and promotes using more widely of martensite antimicrobial stainless steel.
Description of drawings
Fig. 1 is the polarization curve of embodiment 1, and wherein curve 1 is the contrast Martensite Stainless Steel, and curve 2 is a martensite antimicrobial stainless steel
Fig. 2 is the X-ray diffraction curve of embodiment 2
The metallographic structure shape appearance figure that Fig. 3 obtains for embodiment 2
Fig. 4 is embodiment 4 killing colon bacillus effect photos, wherein, and a left side: martensite antimicrobial stainless steel, the right side: contrast 420 class Martensite Stainless Steel
Fig. 5 is the effect photo that embodiment 4 kills streptococcus aureus, wherein, and a left side: martensite antimicrobial stainless steel; Right: contrast 420 class Martensite Stainless Steel
Embodiment
The detection method of martensite antimicrobial stainless steel anti-microbial property is provided: with reference to related standards in following examples; The test strain of selecting for use is intestinal bacteria (Escherichia coli 25922) and streptococcus aureus (Staphylococcus aureus 25923), calculates anti-bacteria stainless steel and control sample (common stainless steel or do not have other solid material of sterilizing ability) according to the following equation to the sterilizing rate after common bacteria (intestinal bacteria, the streptococcus aureus etc.) effect:
Sterilizing rate (%)=[(control sample viable count-anti-bacteria stainless steel viable count)/control sample viable count] * 100
In the formula, the control sample viable count is the viable count that carries out on the control sample after the microbial culture, and the anti-bacteria stainless steel viable count is meant the viable count that carries out on the anti-bacteria stainless steel after the microbial culture.
Following examples also provide the electrochemical test method of martensite antimicrobial stainless steel corrosion resistance nature: adopt conventional electrochemistry three-electrode system method on the CHI660A workstation, sample to be carried out the polarization curve test; Reference electrode is the KCl SCE; Counter electrode is a platinum electrode, and sweep velocity is 0.5mV/s.On metallographic pre-grinding machine, sample is ground to 2000 step by step before the test
#Sand paper, tested media are that concentration is 8.5 ‰ NaCl physiological salt soln, and experimental temperature is 25 ℃.Through testing the corrosion potential of different samples, investigate its corrosion resistance nature.
The reference substance that concrete following examples are selected for use is the 420 class Martensite Stainless Steel.
In the present embodiment, the chemical ingredients of novel martensite antimicrobial stainless steel is (wt) % as follows:
C:0.22, Cr:12.90, Mn:0.41, Si:0.53, P:0.006, S:0.003, Cu:3.22, Mo:0.55, all the other are Fe.
Above-mentioned martensite antimicrobial stainless steel forges rod at 1120 ℃ after vacuum induction is smelted.The thermal treatment process of martensite antimicrobial stainless steel is:
(1) at 1040 ℃ of insulation 0.5h, fully solid solution is in matrix to make copper in the steel, and oil cooling makes the copper in the steel be in hypersaturated state to room temperature;
(2) at 700 ℃ of insulation 6h, make oversaturated copper from steel, separate out the copper-rich phase of q.s, air cooling is to room temperature afterwards;
(3) at 1000 ℃ of insulation 3min, oil cooling is to room temperature;
(4) 150 ℃ of insulation 1h tempering.
To above-mentioned martensite antimicrobial stainless steel; Carry out anti-microbial property according to standard codes such as " JIS Z 2801-2000 " antibiotic fabricated product-bacterinertness TP and antibacterial effect ", GB/T 21510-2008 " nano inorganic material anti-microbial property detection method " " and detect, detected result is: to the sterilizing rate of intestinal bacteria (Eschericher Coli): >=99.9%; Sterilizing rate to streptococcus aureus (Staphyococcus aureus): >=99.9%.Show that the martensite antimicrobial stainless steel among the embodiment 1 has excellent antibacterial.
Martensite antimicrobial stainless steel to present embodiment adopts electrochemical test method to carry out the polarization curve test; Result such as Fig. 1 show; The pitting potential of the cupric molybdenum type martensite antimicrobial stainless steel of present embodiment demonstrates more superior corrosion resistance ability apparently higher than contrast 420 class Martensite Stainless Steel.
In the present embodiment, the chemical ingredients of novel martensite antimicrobial stainless steel is (wt) % as follows:
C:0.22, Cr:12.90, Mn:0.41, Si:0.53, P:0.006, S:0.003, Cu:3.22, Mo:0.55, all the other are Fe.
Above-mentioned martensite antimicrobial stainless steel forges rod at 1120 ℃ after vacuum induction is smelted.The thermal treatment process of martensite antimicrobial stainless steel is:
(1) at 1040 ℃ of insulation 0.5h, fully solid solution is in matrix to make copper in the steel, and water-cooled makes the copper in the steel be in hypersaturated state to room temperature;
(2) at 700 ℃ of insulation 6h, make oversaturated copper from steel, separate out the copper-rich phase of q.s, air cooling is to room temperature afterwards,
(3) through 1000 ℃ of insulation 5min, oil cooling is to room temperature;
(4) 150 ℃ of insulation 1h, tempering.
According to standards such as " JIS Z 2801-2000 " antibiotic fabricated product-bacterinertness TP and antibacterial effect ", GB/T 21510-2008 " nano inorganic material anti-microbial property detection method " ", its detected result is: to the sterilizing rate of intestinal bacteria (Eschericher Coli): >=99.9%; Sterilizing rate to streptococcus aureus (Staphyococcus aureus): >=99.9%, show that the anti-bacteria stainless steel of present embodiment has excellent antibacterial.
Present embodiment is through after the above-mentioned thermal treatment; Visible in Fig. 2: matrix is a martensitic structure; ° locate to occur a new peak in 2 θ=43.09; Corresponding with the diffraction peak of Cu (111), show in this sample and separated out copper-rich phase that this is the prerequisite that martensite antimicrobial stainless steel possesses antimicrobial characteristic.
Embodiment 3:
In the present embodiment, the staple of martensite antimicrobial stainless steel is (wt) %:
C:0.22, Cr:12.90, Mn:0.41, Si:0.53, P:0.006, S:0.003, Cu:3.22, Mo:0.66, all the other are Fe.
Above-mentioned martensite antimicrobial stainless steel forges rod at 1120 ℃ after vacuum induction is smelted, the thermal treatment process of martensite antimicrobial stainless steel is:
(1) at 1040 ℃ of insulation 0.5h, fully solid solution is in matrix to make copper in the steel, and water-cooled makes the copper in the steel be in hypersaturated state to room temperature;
(2) at 700 ℃ of insulation 6h, make oversaturated copper from steel, separate out the copper-rich phase of q.s, air cooling is to room temperature afterwards,
(3) through 1000 ℃ of insulation 3min, oil cooling is to room temperature;
(4) 150 ℃ of insulation 1h, tempering.
According to standards such as " JIS Z 2801-2000 " antibiotic fabricated product-bacterinertness TP and antibacterial effect ", GB/T 21510-2008 " nano inorganic material anti-microbial property detection method " ", its detected result is:
(1) to the sterilizing rate of intestinal bacteria (Eschericher Coli): >=99.9%;
(2) to the sterilizing rate of streptococcus aureus (Staphyococcus aureus): >=99.9%.
In the present embodiment 3; With respect to embodiment 1 and 2; Improved the Mo content in the martensite antimicrobial stainless steel; Through electro-chemical test, the pitting potential of anti-bacteria stainless steel shows further that apparently higher than the corrosion potential of contrast 420 class Martensite Stainless Steel cupric molybdenum type anti-bacteria stainless steel corrosion resistance nature significantly is superior to contrasting stainless steel.
Embodiment 4:
In the present embodiment, the staple of martensite antimicrobial stainless steel is (wt) %:
C:0.22, Cr:12.90, Mn:0.41, Si:0.53, P:0.006, S:0.003, Cu:3.22, Mo:0.66, all the other are Fe.
Above-mentioned martensite antimicrobial stainless steel forges rod at 1120 ℃ after vacuum induction is smelted, the thermal treatment process of martensite antimicrobial stainless steel is:
(1) at 1040 ℃ of insulation 0.5h, fully solid solution is in matrix to make copper in the steel, and water-cooled makes the copper in the steel be in hypersaturated state to room temperature;
(2) at 700 ℃ of insulation 6h, make oversaturated copper from steel, separate out the copper-rich phase of q.s, air cooling is to room temperature afterwards,
(3) through 1000 ℃ of insulation 5min, oil cooling is to room temperature;
(4) 150 ℃ of insulation 1h, tempering.
According to standards such as " JIS Z 2801-2000 " antibiotic fabricated product-bacterinertness TP and antibacterial effect ", GB/T 21510-2008 " nano inorganic material anti-microbial property detection method " ", its detected result is:
(1) to the sterilizing rate of intestinal bacteria (Eschericher Coli): >=99.9%;
(2) to the sterilizing rate of streptococcus aureus (Staphyococcus aureus): >=99.9%.
In accompanying drawing 5, can significantly see sterilization effect.
Present embodiment 4 is compared with first three embodiment; Increased the time of 1000 ℃ of insulations in content and the thermal treatment of Mo; The martensite antimicrobial stainless steel of present embodiment is observed after 10 days in soaking at room temperature through saline water with contrast 420 class Martensite Stainless Steel; Show that cupric molybdenum type martensite antimicrobial stainless steel surface still has gloss, no obvious corrosion phenomenon; And big area uniform corrosion phenomenon appears in contrast 420 class martensitic stainless steel face, shows that corrosion resistance nature of the present invention is superior to contrasting stainless steel.
Claims (4)
1. novel martensite antimicrobial stainless steel, it is characterized in that: by weight percentage, this stainless chemical ingredients is following: C:0.16-0.25; Si:0-1.00%; Mn:0-1.00%; P:0-0.035%; S:0-0.030%; Cr:12.0-14.0%; Cu:2.0-4.0%; Mo:0.5-1.0%; Surplus is Fe.
2. the described a kind of novel martensite antimicrobial stainless steel of claim 1 is characterized in that: Cu:3.0-3.5%; Mo:0.5-0.6%.
3. the heat treating method of the described a kind of novel martensite antimicrobial stainless steel of claim 1 is characterized in that: comprise the steps:
(1) 1000-1100 ℃ solution treatment 0.5-1 hour, oil cooling is to room temperature;
(2) 500-800 ℃ of insulation 2-6 hour, air cooling was to room temperature;
(3) 980-1020 ℃ solution treatment 3-10 minute, oil cooling is to room temperature;
(4) 150-250 ℃ is incubated 1-2 hour, and air cooling is to room temperature.
4. the described a kind of novel martensite antimicrobial stainless steel of claim 1 is in the application of making sanitary apparatus, food utensil, tableware, cutlery and medicine equipment etc.
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Cited By (2)
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| CN102978535A (en) * | 2012-11-22 | 2013-03-20 | 中国科学院金属研究所 | Novel martensite antibacterial stainless steel as well as heat treatment method and application thereof |
| CN106725868A (en) * | 2017-01-13 | 2017-05-31 | 南方医科大学南方医院 | Blood drawing table |
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Cited By (3)
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| CN102978535A (en) * | 2012-11-22 | 2013-03-20 | 中国科学院金属研究所 | Novel martensite antibacterial stainless steel as well as heat treatment method and application thereof |
| CN102978535B (en) * | 2012-11-22 | 2014-12-10 | 中国科学院金属研究所 | Novel martensite antibacterial stainless steel as well as heat treatment method and application thereof |
| CN106725868A (en) * | 2017-01-13 | 2017-05-31 | 南方医科大学南方医院 | Blood drawing table |
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Application publication date: 20120125 |