CN104388842B - A kind of Fe-Cr-B system corrosion block non-crystaline amorphous metal and preparation method thereof - Google Patents
A kind of Fe-Cr-B system corrosion block non-crystaline amorphous metal and preparation method thereof Download PDFInfo
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Abstract
A kind of Fe Cr B system corrosion block non-crystaline amorphous metal and preparation method thereof, belongs to non-crystaline amorphous metal field.The chemical composition of this non-crystaline amorphous metal is designed as by atomic ratio: FeaCrbMocBdMeRfXg.Composition characteristics is: M is one or more in Mn, Co, Ni；R is one or more in Ti, Zr, Nb, Hf, Ta, W；X is one or more elements in Si, P.Wherein, 20 ＜ a≤78,5≤b≤45,0≤c≤20,6≤d≤30,0≤e≤40,2≤f≤15,0≤g≤10, a+b+c+d+e+f+g=100.The feature of alloy of the present invention is with low cost, and the raw material of industry can be used to carry out melting；There is higher Boron contents and good amorphous formation ability simultaneously, be particularly well-suited to nuclear waste material storing and transporting；In alloy, high-Cr then ensure that without C this non-crystaline amorphous metal has the decay resistance of excellence；This non-crystaline amorphous metal also has high compressive strength and microhardness.Therefore, the Fe-based amorphous alloy of the present invention has a good application prospect on metal material anticorrosion, nuclear facilities and wear parts.
Description
Technical field
The invention belongs to non-crystaline amorphous metal field, be specifically related to one and there is high amorphous formation ability, high boron content and highly corrosion resistant
The Fe-Cr-B system non-crystaline amorphous metal of property.
Background technology
Fe-based amorphous alloy due to its cheap cost, preferable glass forming ability, good soft magnet performance, high-wear resistance
And high-corrosion resistance industrially demonstrates important using value.Compare other non-crystaline amorphous metals, can in Fe-based amorphous alloy
To accommodate the highest B atom of content, can be as the neutron-absorbing material of nuke rubbish without there is crystallization, and the interpolation meeting of Cr
It is obviously improved the decay resistance of Fe-based amorphous alloy.Since the iron base amorphous magnetically-soft alloy that continues obtains extensive industrialization, coating is used
The exploitation of wear resistant corrosion resistant Fe-based amorphous alloy has gradually spread out with application.
The highly corrosion resistant of Fe-based amorphous alloy, is firstly because non-crystaline amorphous metal and has phase structure, do not exist crystal boundary, dislocation and
The faults of construction such as fault；Secondly, the activity of amorphous alloy surface atom is the highest, can be on surface containing higher Fe-based amorphous of Cr
On quickly form the most fatal passivating film, make corrosion be difficult to occur.
The basis of northeastern Japan university in 1974 is good for seminar and is found Fe70Cr10P13C7Non-crystaline amorphous metal is at the HCl solution of 1mol/L
In decay resistance be better than traditional 304 rustless steels (Fe-18Cr-8Ni).Japan Patent JPS58113354 discloses one
Planting containing P, C or P, the Fe-Cr-Mo non-crystaline amorphous metal of Si, this non-crystaline amorphous metal shows the decay resistance of excellence in hot hydrochloric acid.
Japan Patent JP3805601 discloses the block amorphous alloy of a kind of Fe-Cr base containing C, high Cr non-crystaline amorphous metal before solving
The problem that amorphous formation ability is not enough, wherein Fe45Cr15Mo15C15B10The critical dimension of non-crystaline amorphous metal reaches 2.5mm, simultaneously
There is the decay resistance of excellence.
United States Patent (USP) US7052561B2 discloses a kind of amorphous steel containing Y, and the interpolation of rare earth element y makes the iron-based containing Cr non-
The critical dimension of peritectic alloy is had been further upgraded, (Fe43Cr16Mo16C15B10)98Y2(Fe45Co5Cr6Mo13Mn11
C16B6)98.5Y1.5The critical dimension of block amorphous alloy respectively reaches 7mm and 12mm.
United States Patent (USP) US8524053B2 discloses the Fe that critical dimension is 9mm48Cr15Mo14C15B6Y2And amorphous formation ability
Poor high boron component Fe49.7Cr18.1Mn1.9Mo7.4W1.6B15.2C3.8Si2.4Non-crystaline amorphous metal, alloy designations is named as respectively
SAM1651 and SAM2X5.SAM2X5 alloy coat shows the decay resistance of excellence in various complex corrosion environment,
There is the neutron absorption capability more more excellent than conventional neutron absorbing material simultaneously.
Up to the present, high Cr corrosion resistant iron base block amorphous alloy all relies on C content higher in composition or rare earth unit
The interpolation of element.The too high fragility that can increase alloy of C content, C occurs enrichment then can accelerate the corrosion of material, is to prepare amorphous to close
The unfavorable factor of gold plating；On the other hand, when C content is higher, the B atomic weight that can accommodate in alloy is inevitable relatively low, is unfavorable for
The neutron absorption capability of material.Adding rare earth element y etc. and can increase cost of material and melting cost, the high activity of rare earth may be right
Alloy corrosion resistance can adversely affect.Therefore develop high Cr, high B, without C and without rare earth iron-base block amorphous alloy have
There is highly important realistic meaning.
Up to now, high B, research without C with without the iron-base block amorphous alloy of rare earth are concentrated mainly on soft magnetic amorphous alloy neck
Territory.The Fe of aboveground bright nine seminars of such as northeastern Japan university exploitation56Co7Ni7Zr10B20(2mm)、
[(Fe0.6Co0.4)0.75B0.2Si0.05]96Nb4(4mm)、[(Fe0.8Ni0.2)0.75B0.2Si0.05]96Nb4(2mm) alloying component such as.These become
Divide all without Cr element, be not suitable for corrosion-resistant purposes.
2009, king built and strong etc. have studied the F using HVAF technology to preparee48Cr15Mo14C15B6Y2Non-crystaline amorphous metal
The performance of coating, they find that this coating has the wear-corrosion resistance of excellence.2011, Zhang Cheng etc. used supersonic flame
Spraying technology is prepared for Fe48Cr15Mo14C15B6Y2Amorphous alloy coating, and have studied dusty spray particle diameter to coating structure and
The impact of the corrosion behavior in simulated seawater environment.2012, Shen Jun etc. used plasma spraying technology to be prepared for
Fe42.87Cr15.98Mo16.33C15.94B8.88Amorphous alloy coating also have studied the decay resistance of coating.
It can be seen that the preparation of above-mentioned wear resistant corrosion resistant iron base amorphous alloy coatings mainly uses the researcher of Japan and the U.S. to open
The composition sent out.The U.S. relies on liquid metal (Liquidmetal) company by wear resistant corrosion resistant Fe-based amorphous alloy commercialization.
The domestic independent intellectual property right that there is no this respect, therefore develops novel wear resistant corrosion resistant iron base non-crystaline amorphous metal to filling the domestic gaps
Significant.
Summary of the invention
Present disclosure is to have developed a kind of high boron content and have the series bulk amorphous conjunction of Fe-Cr-B of high-corrosion resistance
Gold.The feature of alloy of the present invention is with low cost, and the raw material of industry can be used to carry out melting；There is higher Boron contents and good simultaneously
Good amorphous formation ability, is particularly well-suited to nuclear waste material storing and transporting；In alloy, high-Cr then ensure that this non-crystaline amorphous metal without C
There is the decay resistance of excellence.Therefore, the Fe-Cr-B system non-crystaline amorphous metal of the present invention metal material anticorrosion, nuclear facilities and
Have a good application prospect on wear parts.
The chemical composition of the Fe-Cr-B system non-crystaline amorphous metal of the present invention is designed as by atomic ratio: FeaCrbMocBdMeRfXg.Become dtex
Levy for: M is one or more in Mn, Co, Ni；R is one or more in Ti, Zr, Nb, Hf, Ta, W；
X is one or more elements in Si, P.Wherein, 20 ＜ a≤78,5≤b≤45,0≤c≤20,6≤d≤30,0≤e
≤ 40,2≤f≤15,0≤g≤10, a+b+c+d+e+f+g=100.
In above-mentioned alloy, as c=e=g=0, described alloy composition is represented by FeaCrbBdRf, its composition range is expressed as
40≤a≤75,5≤b≤38,10≤d≤25,4≤f≤15, a+b+d+f=100.
Working as e=g=0, R when being defined to Zr element, described alloy composition is represented by FeaCrbMocBdZrf, its composition range table
It is shown as 30≤a≤75,5≤b≤40,0 ＜ c≤20,7≤d≤28,2≤f≤15, a+b+c+d+f=100.
At above-mentioned FeaCrbMocBdZrfIn alloy, alloying component can be further preferred, and its composition range is expressed as 52≤a≤66,
8≤b≤11,5≤c≤10,15≤d≤19,6≤f≤8, a+b+c+d+f=100, this non-crystaline amorphous metal critical dimension reaches 3mm.
At above-mentioned FeaCrbMocBdZrfIn alloy, alloying component can be further preferred, and its composition range is expressed as 35≤a≤57,
25≤b≤40,0 ＜ c≤6,11≤d≤16,6≤f≤8, a+b+c+d+f=100, this non-crystaline amorphous metal has the most outstanding corrosion resistant
Erosion performance.
When M is defined to Co element, described alloy composition is represented by FeaCrbMocBdCoeRfXg, its composition range represents
It is 20 ＜ a≤75,5≤b≤40,0≤c≤20,7≤d≤28,0 ＜ e≤40,2≤f≤15,0≤g≤10,
A+b+c+d+e+f+g=100.
At above-mentioned FeaCrbMocBdCoeRfXgIn alloy, alloying component can more preferably FeaCrbBdCoeZrfSig, it becomes
Dividing Range Representation is 21≤a≤35,8≤b≤11,17≤d≤19,30≤e≤40,6≤f≤8,2≤g≤4,
A+b+d+e+f+g=100, this non-crystaline amorphous metal critical dimension reaches 3mm.
When M is defined to Ni element, described alloy composition is represented by FeaCrbMocBdNieRfXg, its composition range is expressed as
30≤a≤75,5≤b≤40,0≤c≤20,7≤d≤28,0 ＜ e≤25,2≤f≤15,0≤g≤10,
A+b+c+d+e+f+g=100.
Block amorphous alloy preparation method of the present invention includes: the purity of raw material Fe, Co or Ni that (1) uses is the lowest
In 99.5%, the purity of Cr or Si is not less than 99%, B or Mo adds with the form of industry ferro-boron or industry molybdenum-iron respectively, its
The purity of remaining raw material is not less than 99.9%；(2) use sand paper and abrasive machine to remove the surface scale of raw metal, according to mole
Than carrying out accurate weighing proportioning and using EtOH Sonicate ripple to clean raw material；(3) vacuum non-consumable tungsten electrode arc melting is used to close
Gold, is evacuated to vacuum≤1 × 10 to body of heater-2Pa, is filled with pure argon until furnace pressure reaches 0.4-0.5 atmospheric pressure；(4)
Alloy melting 3-5 time, it is ensured that melting is uniform；(5) after alloy melting completes, polishing scale removal with abrasive machine, it is suitable to take
Weight dehydrated alcohol ultrasonic cleaning, re-uses the supporting suction pouring equipment of electric arc furnace and copper mold is prepared cylindrical block amorphous and closed
Gold.
The iron-base block amorphous alloy of the present invention has mechanical property and the decay resistance of excellence.Fe57Cr12Mo5Zr8B18Block
The intensity of non-crystaline amorphous metal is more than 4GPa, Fe57Cr18Mo2Zr8B15And Fe43Cr35Mo2Zr8B12The micro Vickers of block amorphous alloy
Hardness number is respectively 1161 and 1226.Fe57Cr18Mo2Zr8B15Block amorphous alloy corrodes electricity in the hydrochloric acid of 1moL/L certainly
Position is-193.4mV, and corrosion rate is 6.3 μm/year；Fe43Cr35Mo2Zr8B12Block amorphous alloy is at the hydrochloric acid of 1moL/L
In corrosion potential be 15.6mV, corrosion rate is 2.6 μm/year.The decay resistance of non-crystaline amorphous metal is along with Cr content
Increase and improve, be much better than tradition crystalline material 316L rustless steel.
Accompanying drawing explanation
Fig. 1 is the Fe of the diameter 3mm of the present invention57Cr10Mo7Zr8B18The X ray diffracting spectrum (copper target) of block amorphous alloy.
Fig. 2 is the Fe of the diameter 1mm of the present invention43Cr35Mo2Zr8B12And Fe67Cr10Nb4B16Si3The X of block amorphous alloy penetrates
Ray diffraction diagram spectrum (molybdenum target).
Fig. 3 is the changing trend diagram that the FeCrZrB block amorphous alloy critical dimension of the present invention increases with Cr content.
Fig. 4 is the Fe of the present invention65Cr10(Zr6-xNbx)B16Si3Block amorphous alloy critical dimension is with the change of Zr, Nb changes of contents
Change trendgram.
Fig. 5 is the changing trend diagram that the FeCrMoZrB block amorphous alloy critical dimension of the present invention increases with Cr content.
Fig. 6 is the Fe of the present invention67-xCrxMo7Zr8B18The changing trend diagram that block amorphous alloy critical dimension increases with Cr content.
Fig. 7 is the Fe of the present invention64-xCr10MoxZr8B18The variation tendency that block amorphous alloy critical dimension increases with Mo content
Figure.
Fig. 8 is the Fe of the present invention65-xCr10Mo7ZrxB18The changing trend diagram that block amorphous alloy critical dimension increases with Zr content.
Fig. 9 is the Fe of the present invention75-xCr10Mo7Zr8BxThe changing trend diagram that block amorphous alloy critical dimension increases with B content.
Figure 10 is the FeCrMoZrBSi of the present inventionxThe changing trend diagram that block amorphous alloy critical dimension increases with Si content.
Figure 11 is the Fe of the present invention73-xCrxMo2Zr6B16Si3The variation tendency that block amorphous alloy critical dimension increases with Cr content
Figure.
Figure 12 is the Fe of the present invention65-xCr10MoxZr6B16Si3The change that block amorphous alloy critical dimension increases with Mo content becomes
Gesture figure.
Figure 13 is the Fe of the present invention65-xCoxCr8Mo2Zr6B16Si3The change that block amorphous alloy critical dimension increases with Co content
Trendgram.
Figure 14 is the Fe of the present invention57Cr10Mo7Zr8B18The DSC curve figure of block amorphous alloy.
Figure 15 is the Fe of the present invention57Cr10Mo7Zr8B18And Fe57Cr12Mo5Zr8B18Compression stress-the strain of block amorphous alloy
Curve chart.
Figure 16 is the Fe of the present invention57Cr18Mo2Zr8B15And Fe43Cr35Mo2Zr8B12Block amorphous alloy is in 1mol/L hydrochloric acid
Cyclic polarization curve chart.
Detailed description of the invention
The present invention is specifically introduced below in terms of composition design, alloy preparation and performance test three.
1, composition design
The Fe of design heterogeneityaCrbMocBdMeRfXgAlloy, its composition characteristics is: M is the one in Mn, Co, Ni
Or it is multiple；R is one or more in Ti, Zr, Nb, Hf, Ta, W；X is one or more in Si, P.Wherein,
20 ＜ a≤78,5≤b≤45,0≤c≤20,6≤d≤30,0≤e≤40,2≤f≤15,0≤g≤10,
A+b+c+d+e+f+g=100.
Fe, Cr are the basic constituent element of alloy system, and B element is indispensable amorphous formation element；Zr, Nb are and major components
Having the thick atom of the big negative heat of mixing, can carry heavy alloyed amorphous formation ability further, Ti, Hf, Ta, W are as closely
Neighbors can partial replacement.Design composition FeaCrbBdRf。
As the congeners of Cr, the addition of Mo can put forward heavy alloyed amorphous formation ability and mechanical property further, simultaneously
Add Mo and can further enhance the decay resistance especially corrosion-resistant ability of alloy.Zr is thick atom, with Fe, Cr, Mo,
There is the bigger negative heat of mixing between B, be one of critical elements improving alloy amorphous Forming ability.Design composition
FeaCrbMocBdZrf。
Co is the similar element of Fe, designs composition FeaCrbMocBdCoeRfXg, the addition of research Co is to alloy amorphous formation energy
The impact of power.
Ni is the similar element of Fe, designs composition FeaCrbMocBdNieRfXg, the addition of research Ni is to alloy amorphous formation energy
The impact of power.
2, prepared by alloy
Dispensing: the purity of raw material Fe, Co or Ni of use is not less than 99.5%, the purity of Cr or Si is not less than 99%, B or
Mo is provided by industry ferro-boron or industry molybdenum-iron respectively, and the purity of remaining raw metal is not less than 99.9%.According to the composition set,
Accurate weighing proportioning raw material is carried out according to mol ratio.The industrial ferro-boron used and industry molybdenum-iron main component and impurity are shown in Table 1.
Table 1 tests the industrial ferro-boron used and the main chemical compositions (wt%) of industry molybdenum-iron
Prepared by alloy bar: use vacuum non-consumable tungsten electrode arc melting alloy, body of heater is evacuated to vacuum≤1 × 10-2Pa,
It is filled with pure argon until furnace pressure reaches 0.4-0.5 atmospheric pressure.For ensureing that the abundant melting of alloy is uniform, containing difficulties such as Nb, W
Composition elder generation melting Fe-Nb, Fe-W intermediate alloy of molten metal.Foundry alloy needs abundant molten alloy 3-5 all over down to uniformly.From molten
Refine the alloy taking appropriate mass on uniform foundry alloy, inhaled by suction pouring equipment after melting in non-consumable tungsten electrode electric arc furnace
It is cast into, into the fast cold forming of copper mold, according to the difference of composition, preparing the alloy bar of a diameter of 1-4mm.
3, alloy performance test
1) X-ray diffraction (XRD) test
Using X-ray diffractometer that sample is carried out crystal species analysis, for convenience of test, the sample of different-diameter uses different surveys
Examination equipment, diameter 2mm and above sample use Cu target XRD testing equipment, scanning step 0.02s-1, scan angle
Spend the scope of 2 θ from 10 ° to 90 °；Diameter 1.5mm and following sample use Mo target XRD testing equipment.
Accompanying drawing 1 is the Fe of diameter 3mm57Cr10Mo7Zr8B18The XRD curve (Cu target) of alloy bar, curve table reveals one
Wide in range steamed bread peak, without crystal peak, shows that test sample is amorphous state.
Accompanying drawing 2 is the Fe of diameter 1mm43Cr35Mo2Zr8B12And Fe67Cr10Nb4B16Si3The XRD curve (Mo target) of alloy bar,
Article two, curve all shows wide in range steamed bread peak, without crystal peak, shows that test sample is amorphous state.
Accompanying drawing 3 shows the impact of Cr changes of contents Forming ability alloy amorphous on FeCrZrB, in conjunction with table 1 it can be seen that with
Cr content increases, and the critical dimension of alloy shows the trend of first increases and then decreases, when Cr content superelevation 40%, it is impossible to obtain
Obtain block amorphous alloy.As it can be seen from table 1 along with the raising of Cr content, the B content of alloying component is gradually lowered,
This is consistent with the eutectic point variation tendency of Fe-Cr-B phasor.
Accompanying drawing 4 shows replaces Zr to Fe with Nb65Cr10(Zr6-xNbx)B16Si3The impact of alloy amorphous Forming ability.From figure
It can be seen that along with Nb content increases, the amorphous formation ability first increases and then decreases of alloy, Zr with Nb is similar thick atom,
Full Zr or full Nb composition all can obtain block amorphous alloy.
Table 1FeCrZrB alloying component and amorphous formation ability thereof
Table 2FeCrMoZrB alloying component and amorphous formation ability thereof
Accompanying drawing 5 shows the impact on FeCrMoZrB block amorphous alloy amorphous formation ability of the Cr changes of contents, in conjunction with table 2
It can be seen that similar with composition FeCrZrB, increase with Cr content, the critical dimension of alloy shows becoming of first increases and then decreases
Gesture, when Cr content reaches 45%, it is impossible to obtain block amorphous alloy.Equally, along with the raising of Cr content, alloying component
B content be gradually lowered.In conjunction with accompanying drawing 1 it is found that the bulk amorphous alloy that the interpolation of Mo greatly improves alloy closes
The forming range of gold and critical dimension, make it be more nearly eutectic composition simultaneously this is because the interpolation of Mo reduces alloy melting point
Add the alloy randomness when liquid.
Accompanying drawing 6 shows that Cr changes of contents is to Fe67-xCrxMo7Zr8B18The impact of block amorphous alloy amorphous formation ability, with
The increase of Cr content, the critical dimension of alloy shows the trend of first increases and then decreases, when Cr content is 10, the amorphous of alloy
Forming ability is more excellent.
Accompanying drawing 7 shows that Mo changes of contents is to Fe64-xCr10MoxZr8B18The impact of block amorphous alloy amorphous formation ability, with
The increase of Mo content, the critical dimension of alloy shows the trend of first increases and then decreases, Mo content when 5～9, alloy
Amorphous formation ability is more excellent.
Accompanying drawing 8 shows that Zr changes of contents is to Fe65-xCr10Mo7ZrxB18The impact of block amorphous alloy amorphous formation ability, with
The increase of Mo content, the critical dimension of alloy shows the trend of first increases and then decreases, Zr content when 6～8, alloy
Amorphous formation ability is more excellent.
Accompanying drawing 9 shows that B content changes Fe75-xCr10Mo7Zr8BxThe impact of block amorphous alloy amorphous formation ability, with B
The increase of content, the critical dimension of alloy shows the trend of first increases and then decreases.When B content is 8, still can obtain
Bulk amorphous alloy, this is the iron-base block amorphous alloy that current metalloid content is minimum.When B content is between 14～18, alloy
Amorphous formation ability is more excellent.
Accompanying drawing 10 shows that Si's adds the impact on FeCrMoZrB block amorphous alloy amorphous formation ability, the interpolation meeting of Si
Causing alloy to deviate eutectic composition, the amorphous formation ability to alloy is disadvantageous, but affects less generally.Part adds Si
Alloying component and amorphous formation ability be shown in Table 3.
Table 3FeCrMoZrBSi alloying component and amorphous formation ability thereof
Accompanying drawing 11 shows that Cr changes of contents is to Fe73-xCrxZr6Mo2B16Si3The impact of block amorphous alloy amorphous formation ability,
With the increase of Cr content, the amorphous formation ability of alloy is gradually lowered.
Accompanying drawing 12 shows that Mo changes of contents is to Fe65-xCr10MoxZr6B16Si3The impact of block amorphous alloy amorphous formation ability,
With the increase of Mo content, the critical dimension of alloy shows the trend of first increases and then decreases.
Co is the most like element of Fe, and Co replacement in Fe base noncrystal alloy is very universal, and tends to improve alloy
Amorphous formation ability.The alloying component and the amorphous formation ability thereof that partly add Co are shown in Table 4, it can be seen that Fe is replaced by Co
Change the amorphous formation ability to alloy and have obvious advantageous effect, alloy open ended B atom content can be improved simultaneously.
Accompanying drawing 13 shows that the replacement of Co is to Fe65-xCoxCr8Mo2Zr6B16Si3The impact of block amorphous alloy amorphous formation ability,
With the increase of Co content, the critical dimension of alloy shows the trend of first increases and then decreases.But combine table 4 it is found that
When improving B content, the critical dimension of non-crystaline amorphous metal significantly improves.So, the interpolation of the Co amorphism to alloy generally
One-tenth ability is favourable.
Ni is the similar element of Fe, and in some Fe-based amorphous alloy system, the amorphous formation ability to alloy that adds of Ni is to have
Profit, but containing in Cr Fe-based amorphous alloy, the interpolation of Ni rarely has report.Find in our study, the interpolation of Ni
The amorphous formation ability of alloy there is obvious adverse effect.Add Ni amorphous alloy component and amorphous formation ability is shown in Table 5.
Table 4 is containing Co alloying component and amorphous formation ability thereof
Table 5 is containing Ni alloying component and amorphous formation ability thereof
Table 6 alloying component and amorphous formation ability thereof
At aforementioned FeaCrbMocBdMeRfXgIn alloy, other metallic elements such as Al, Ti, V, Mn, Cu, Ga, Sn,
The appropriate interpolation of Hf, Ta, W etc. all can form block amorphous alloy, compares metalloid Si, and the adverse effect adding P is the most aobvious
Write.Alloy part composition and amorphous performance capability example thereof are shown in Table 6.
2) differential scanning calorimetry (DSC) is analyzed
Using differential scanning calorimeter that non-crystaline amorphous metal sample is carried out Thermodynamic Analysis, heating rate is 20K/min, heats up
Scope is 300K-1600K.
Accompanying drawing 14 is the Fe recorded57B18Zr8Cr10Mo7The DSC curve of block amorphous alloy, can be seen that from DSC curve
The distinctive supercooling liquid phase region of non-crystalline material, the thermodynamic parameter of part block amorphous alloy is as shown in table 7.
The thermodynamic parameter of table 7 iron-base block amorphous alloy
3) quasistatic compression test
The non-crystaline amorphous metal coupon of preparation is intercepted and is polished into the compression sample that draw ratio is 2:1, it is ensured that two end faces smooth and with
Axially vertical, CMT 4305 type universal electrical testing machine carries out room temperature compression verification, compression speed is 2 × 10-4s-1, often
Kind of alloying component is minimum to be chosen 3 samples and tests.
Accompanying drawing 15 is Fe57B18Zr8Cr10Mo7And Fe57B18Zr8Cr12Mo5The compressive stress strain curve of block amorphous alloy,
It can be seen that Fe57B18Zr8Cr10Mo7The compressive strength of block amorphous alloy about 3.6GPa, elastic deformation amount about 1.8%,
Elastic modelling quantity is 202GPa；Fe57B18Zr8Cr12Mo5The compressive strength of block amorphous alloy is more than 4GPa, and elastic deformation amount is about
2%, elastic modelling quantity is 208GPa.
4) micro-hardness testing
Micro Vickers is tested Fe57Cr18Mo2Zr8B15And Fe43Cr35Mo2Zr8B12Block amorphous alloy micro-firmly
Degree, loading force is 200g, and test environment temperature is 20 DEG C.
Test records Fe57Cr18Mo2Zr8B15The micro Vickers hardness value of block amorphous alloy is 1161 (11.39GPa),
Fe43Cr35Mo2Zr8B12The micro Vickers hardness value of block amorphous alloy is 1226 (12.02GPa).Test result shows both
Block amorphous alloy is respectively provided with high microhardness, and the microhardness of material can reflect its anti-wear performance, in general, micro-
The anti-wear performance of the highest material of hardness is the best.Although the metalloid B content of Cr35 composition is relatively low, but due to Cr content in composition
The highest, its microhardness is the highest compared with Cr18 composition.
5) electro-chemical test
At the cyclic polarization curve of electrochemical workstation test block amorphous alloy, reference electrode is saturated calomel electrode, corrodes molten
Liquid is the hydrochloric acid solution of 1mol/L, and test environment temperature is 30 DEG C, and testing sample surface need to be processed by shot blasting.According to ASTM
The testing standard of cyclic polarization curve, scanning current potential, from the beginning of relative OCP-300mV, reaches 1mA/cm to electric current density2
Time, start negative direction electric potential scanning, until current potential reaches to terminate during relative OCP-300mV, scanning speed 1mV/s.
Cyclic polarization curve from accompanying drawing 16 is it can be seen that Fe57Cr18Mo2Zr8B15And Fe43Cr35Mo2Zr8B12Bulk amorphous alloy
Alloy all shows the decay resistance of excellence in the hydrochloric acid solution of 1mol/L.Fe57Cr18Mo2Zr8B15Non-crystaline amorphous metal is 1
Corrosion potential in the hydrochloric acid solution of mol/L is-193.4mV, and corrosion rate is 6.3 μm/year, ties up blunt electric current density and is less than
5×10-5A/cm2, the spot corrosion generation when current potential reaches about 925mV, passivating film be destroyed, protection potential is 870mV.
Fe43Cr35Mo2Zr8B12Non-crystaline amorphous metal corrosion potential in the hydrochloric acid solution of 1mol/L is 15.6mV, and corrosion rate is 2.6
μm/year, ties up blunt electric current density less than 1 × 10-5A/cm2, the spot corrosion generation when current potential reaches about 935mV, passivating film are broken
Bad, protection potential is 910mV.
Table 8 is Fe57Cr18Mo2Zr8B15And Fe43Cr35Mo2Zr8B12Block amorphous alloy is electricity in the hydrochloric acid solution of 1mol/L
Chemical property parameter, 316L rustless steel is as a comparison.
Table 8 electrochemical parameter
Wherein, EcorrFor corrosion potential, for the current potential that anode reaction general speed is equal with cathode reaction general speed, represent corrosion
The complexity started；icorrFor corrosion current density, can be converted into corrosion rate；V is corrosion rate；EbFor breaking up current potential,
It it is the current potential that passivating film is destroyed, spot corrosion occurs；EpFor protection potential, with the electricity of anode flowpath intersection point when being cyclic polarization flyback
Position, characterizes the material self-repairing capability at spot corrosion generation post-passivation film.Outside divided by upper parameter, tie up blunt electric current density ipassAlso it is
The important parameter of evaluation material corrosion resistance, but it is not constant under many circumstances, so being the most individually given.
Owing to 316L rustless steel corrodes comparatively fast in hydrochloric acid, do not exist and break up current potential and protection potential.Correction data it is found that
Above two non-crystaline amorphous metal decay resistance in hydrochloric acid is far superior to conventional crystalline material 316L rustless steel.
The above is ultimate principle and the main feature of the present invention.Above-mentioned embodiment limits the present invention never in any form, right
Embodiment of above does technical scheme that simple transformation obtained all within protection scope of the present invention.
Claims (7)
1. the series bulk amorphous alloy of Fe-Cr-B, its composition is expressed as FeaCrbBdRf, it is characterised in that 40≤a≤75,5≤b
≤ 38,10≤d≤25,4≤f≤15, a+b+d+f=100, R be the one in Ti, Zr, Nb, Hf, Ta, W or
Multiple.
2. the series bulk amorphous alloy of Fe-Cr-B, its composition is expressed as FeaCrbMocBdZrf, it is characterised in that 30≤a≤75,5
≤ b≤40,0 ＜ c≤20,7≤d≤28,2≤f≤15, a+b+c+d+f=100.
A kind of series bulk amorphous alloy of Fe-Cr-B the most according to claim 2, its composition is expressed as FeaCrbMocBdZrf, its
It is characterised by 52≤a≤66,8≤b≤11,5≤c≤10,15≤d≤19,6≤f≤8, a+b+c+d+f=100, should
Non-crystaline amorphous metal critical dimension reaches 3mm.
A kind of series bulk amorphous alloy of Fe-Cr-B the most according to claim 2, its composition is expressed as FeaCrbMocBdZrf, its
It is characterised by 35≤a≤57,25≤b≤40,0 ＜ c≤6,11≤d≤16,6≤f≤8, a+b+c+d+f=100, should
Non-crystaline amorphous metal has the most outstanding decay resistance.
5. the series bulk amorphous alloy of Fe-Cr-B, its composition is expressed as FeaCrbBdCoeZrfSig, it is characterised in that 21≤a≤35,
8≤b≤11,17≤d≤19,30≤e≤40,6≤f≤8,2≤g≤4, a+b+d+e+f+g=100, this non-crystaline amorphous metal
Critical dimension reaches 3mm.
6. the series bulk amorphous alloy of Fe-Cr-B, its composition is expressed as FeaCrbMocBdNieRfXg, it is characterised in that 30≤a≤
75,5≤b≤40,0≤c≤20,7≤d≤28,0 ＜ e≤25,2≤f≤15,0≤g≤10, a+b+c+d+e+f+g=100,
R is one or more in Ti, Zr, Nb, Hf, Ta, W；X is one or more elements in Si, P.
7. the method preparing one of claim 1-6 series bulk amorphous alloy of described Fe-Cr-B, it is characterised in that: (1) makes
The purity of raw material Fe, Co or Ni be not less than 99.5%, the purity of Cr or Si is not less than 99%, B or Mo is respectively
Adding with the form of industry ferro-boron or industry molybdenum-iron, the purity of remaining raw material is not less than 99.9%；(2) use vacuum non-self
Consumption tungsten electrode arc melting alloy, is evacuated to vacuum≤1 × 10 to body of heater-2Pa, is filled with pure argon until stove is intrinsic pressure
Power reaches 0.4-0.5 atmospheric pressure；(3) alloy melting 3-5 time, it is ensured that melting is uniform；(4) after alloy melting completes,
Cylindrical block non-crystaline amorphous metal prepared by suction pouring equipment and copper mold that use electric arc furnace is supporting.
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