CN109930086A - A kind of iron-base block amorphous state alloy and preparation method thereof with high corrosion resistance - Google Patents
A kind of iron-base block amorphous state alloy and preparation method thereof with high corrosion resistance Download PDFInfo
- Publication number
- CN109930086A CN109930086A CN201910158875.7A CN201910158875A CN109930086A CN 109930086 A CN109930086 A CN 109930086A CN 201910158875 A CN201910158875 A CN 201910158875A CN 109930086 A CN109930086 A CN 109930086A
- Authority
- CN
- China
- Prior art keywords
- test tube
- alloy
- quartz test
- special
- corrosion resistance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Investigating And Analyzing Materials By Characteristic Methods (AREA)
Abstract
The invention discloses a kind of iron-base block amorphous state alloy and preparation method thereof with high corrosion resistance, is realized by following below scheme: being Fe by ingredient65Cr10Mo5P13C7Block master alloy and mass ratio be 1:3 CaO and B2O3Powder mixture is put in quartz test tube together, is then placed in the high temperature furnace of 1200oC and is carried out purification processes, and pressure is maintained at 50 Pa or so in quartz test tube in purification process, and the purification time is 4 hours.The rodlike Fe that diameter is 1 millimeter is made by J-quenching technology in alloy after purification processes65Cr10Mo5P13C7Bulk amorphous alloy.The invention has the characteristics that quartz test tube is conducive to the formation of bulk amorphous alloy as container, and method is simple and easy, and cost is not high.Resulting Fe is found through experiments that65Cr10Mo5P13C7Bulk amorphous alloy shows big corrosion resistance (0.0425 mm/y of sample etches speed).It is a kind of very promising anticorrosive candidate material.
Description
Technical field
The invention belongs to bulk amorphous alloy and its in the technical field of improved corrosion performance field application, relate to the use of
Oxide purification technique and quartz test tube blow casting technology and prepare grinding for iron-base block amorphous state alloy and its improved corrosion performance
Study carefully.
Background technique
From nineteen ninety-five, first piece of iron-based (Fe-Al-Ga-P-C-B) bulk amorphous alloy is reported out by Inoue group
Afterwards, iron-base block amorphous state alloy is due to low in cost, so that many concerns are caused in science and engineering field, refering to
1427-1433 pages of the phase of Materials transactions-JIM the 36th.Since bulk amorphous alloy is in function and structure material
Material aspect there is potential value, constantly study and report and close with the iron-base block amorphous state of corrosion resistance by scientists
Gold.In order to extend application of the iron-base block amorphous state alloy in real life, the especially application under rugged environment,
The research of corrosion resistance is with regard to particularly important.Research accordingly, with respect to iron-base block amorphous state alloy corrosion resistance has attracted more
Attention.
The corrosion resistance of iron-based non-crystalline alloy is not only related with the structure of alloy, while and the and close phase of alloying component
It closes.It is well known that Cr, Mo are corrosion resistance elements, and excess Mo is harmful to the corrosion resistance of iron-based non-crystalline alloy.And
And found in the work of early stage, Mo is added in the Fe-P-C amorphous alloy comprising Cr or not comprising Cr, can effectively mention
The corrosion resistance of high alloy illustrates that two kinds of elements of Cr, Mo can show synergistic effect, closes so as to further increase amorphous state
The corrosion resistance of gold, refering to 2137-2151 pages of the phase of Corros. Sci the 38th.Although some iron-based non-with highly corrosion resistant
Crystal alloy is successfully prepared, but since they have low vitrifying Forming ability, leads to the conjunction for being only limitted to strip and film
At refering to J. Non-Cryst. Solids28th 403-413 pages of the phase.In recent years, some so-called with high glass forming ability
Based bulk metallic glasses found out successively, such as Fe-Cr-Mo-C-B-P, refering to J. Electrochem. Soc
179 the 366-369 pages of phases, Fe-Cr-Mo-C-B are refering to 701-704 pages of the phase of J. Mater. Res the 17th etc., but Cr, Mo are to iron-based
The mechanism report of bulk amorphous alloy corrosion resistance is seldom.Therefore, for alloy becomes as corrosion resistant structural material
May, just expectation synthesizes some new iron-base block amorphous state alloys with high-vitrification Forming ability and highly corrosion resistant.
By Flux and J-quenching technology, our research groups have been successfully prepared diameter up to the Fe- of 6 mm
Mo-P-C bulk amorphous alloy, with high vitrifying Forming ability.Therefore, this part work is based on this research knot
Fruit, has investigated Cr, and Mo element individually adds and when collective effect, to Fe80- x-yCrxMoyP13C7Bulk amorphous alloy corrosion resistant
The influence of corrosion.
In addition, also fewer to the research of amorphous alloy improved corrosion performance material in recent years.And bulk amorphous conjunction
Gold has biggish vitrifying Forming ability, can be prepared into the material of suitable shape to meet the needs of design, thus block is non-
Brilliant improved corrosion performance has excellent Research Prospects.
Summary of the invention
Present invention aims at provide one kind in conjunction with Fluxing purification technique and J-quenching technology
Fe65Cr5Mo10P13C7The preparation method of bulk amorphous alloy.The alloy has high corrosion resistance, this work can inspire
Numerous scholars and engineer develop for improved corrosion performance iron block body amorphous alloy material.
The present invention is realized by following technique:
(1) precision balance is utilized, Fe powder (AlfaAesar company, mass percent 99%), Mo powder (AlfaAesar company,
Mass percent is 99.9 %), Cr powder (AlfaAesar company, mass percent are 99.9 %), Fe3P(AlfaAesar company,
Mass percent is 99.5 %), C powder (AlfaAesar company, mass percent be 99.9 %), according to preset alloy at
Divide correct weighing, meets Fe65Cr5Mo10P13C7(wherein ratio is atomic percent)；(2) load weighted raw material is packed into quartz
It is evacuated down to about 50 Pa in test tube, the high-purity argon gas of slightly below one atmospheric pressure is then passed through in quartz test tube as protection
Atmosphere fuses component therein by firelock heated quartz test tube, is prepared into alloy mother's ingot；(3) pass through Flux purification technique
(time is at least 4 h, and purification temperature is maintained at 1200 oC or more) is purified, to reduce the impurity in alloy sample, and is made
Its ingredient is uniform；(4) (special stone will be put into special quartz test tube by Flux purification technique treated alloy sample
English test tube is by thick quartz test tube that an outer diameter is 15 mm/ wall thickness, 1 mm and an outer diameter be 2 ~ 5 mm/ wall thickness about 0.1 ~
The thin-walled fine quartz test tube of 0.3 mm, which is connected, to be constituted).Special quartz test tube passes through a triple valve and mechanical pump and argon bottle phase
Even.Special quartz test tube and mechanical pump are connected by triple valve first, it is extracted into the air pressure of about 50 Pa, then passes through three
Port valve connects it with argon bottle, with the special quartz test tube of argon cleaning, restores persistently to take out special quartz test tube after the completion true
It is empty.Repeatedly three times, it is excluded with the air overwhelming majority ensured in special quartz test tube.Finally into special quartz test tube
Be filled with the argon gas of slightly below one atmospheric pressure, with firelock on the top of special quartz test tube by alloy melting, then with 1.5 ×
105 The alloy of melting is blown into the lower part fine needle of special quartz test tube by the argon gas of Pa, and is heated using firelock to alloy sample,
To ensure that alloy sample is in a molten state.Then special quartz test tube is inserted into cold water rapidly, keeps molten alloy sample fast
Quickly cooling but, to obtain columnar block amorphous alloy.By control special quartz test tube lower part thin-walled quartz test tube it is straight
Diameter and wall thickness can control the cooling rate of alloy sample.
Present invention is characterized in that inertia quartz test tube is conducive to the formation of bulk amorphous alloy, and side as container
Method is simple and easy, and cost is not high.When according to the collective effect of experiment discovery Cr and Mo, alloy corrosion speed is respectively less than individually addition
The corrosion rate of alloy when Cr or Mo, when adding both corrosion resistance elements of Cr and Mo, the Cr component content the more more are conducive to
The raising of bulk amorphous alloy corrosion resistance.Resulting Fe65Cr5Mo10P13C7Bulk amorphous alloy shows big highly resistance
Corrosivity (0.0425 mm/y of sample etches speed) is a kind of very promising improved corrosion performance candidate material.
Detailed description of the invention
Fig. 1 is that quartz test tube blows casting Experimental equipment in example 1.
Fig. 2 is 1 gained Fe of example80-xCrxP13C7And Fe80-xMoxP13C7The X-ray diffractogram of bulk amorphous alloy.
Fig. 3 is 1 gained Fe of example80-x(Cr, Mo)xP13C7The X-ray diffractogram of bulk amorphous alloy.
Fig. 4 is 1 gained Fe of example80-xCrxP13C7Electrokinetic potential of the bulk amorphous alloy in 1 mole of every liter of hydrochloric acid solution
Polarization curve.
Fig. 5 is 1 gained Fe of example80-xM0xP13C7Electrokinetic potential of the bulk amorphous alloy in 1 mole of every liter of hydrochloric acid solution
Polarization curve.
Fig. 6 is 1 gained Fe of example80-x(Cr, Mo)xP13C7Bulk amorphous alloy is in 1 mole of every liter of hydrochloric acid solution
Dynamic potential polarization curve.
Specific embodiment
Embodiment 1
Using precision balance, the element of component alloy is correctly weighed according to the alloying component of setting, after high-purity argon gas protection
Make their alloys to together with firelock under atmosphere；Alloy is placed in quartz test tube together with the oxide of purification, passes through fire
Rifle heated quartz test tube, metal is by B2O3The purification of 4 h is carried out with package in CaO melt medium.After purification process terminates,
Sample is put into that front end is uniform, in the very thin special quartz test tube in tail portion, vacuumizes to it and reaches about 50 Pa.Then pass through threeway
Valve is passed through the argon gas for being slightly less than an atmospheric pressure into special quartz test tube.Alloy mother's ingot is placed on special quartz test tube later
The thick quartz test tube position in portion makes its fusing with firelock heating.After alloy molten solution sufficiently melts, rapidly to special quartz test tube
In be passed through 1.5 × 105The argon gas of Pa, punching press of the alloy molten solution by argon gas, into the fine needle of special quartz test tube front end
Shape part is put into high temperature furnace and keeps the temperature 30 seconds to one minute, then rapidly test tube into the water, make the fast quickly cooling of alloy molten solution
But, Fe is obtained80-x(Cr, Mo)xP13C7Bulk amorphous alloy bar.The X-ray diffractogram of resulting 1 mm sample of different-diameter
Analysis the result shows that, sample X diffraction pattern as shown in Figures 2 and 3 is diffusing scattering packet, and there is no sharp crystallization peaks to occur, and is said
Its bright microstructure is complete amorphous state, and the measurement of corrosion rate is immersed in 1 mole of every liter of hydrochloric acid solution by sample
Of poor quality before and after 168 hours and obtain.Electro-chemical test is using by working electrode (sample), auxiliary electrode (platinum electrode)
With the three-electrode system of reference electrode (K/KCl) composition.Three electrodes stand 40 minutes or so in 1 M HCl solution, make to open a way
After current potential is basicly stable, dynamic potential polarization curve is measured under the potential scan rate of 1 mV/s.Before testing, the work of sample
Surface first has to carry out grinding process with No. 2400 sand paper, is then cleaned with deionized water and naturally dry is spare.Such as Fig. 4 institute
Show the Fe of different Cr ingredients80-xCrxP13C7The dynamic potential polarization curve of bulk amorphous alloy.It can be seen from the figure that in addition to
Fe80P13C7Bulk amorphous alloy, the bulk amorphous alloy containing Cr all show spontaneous blunt in 1 mole of every liter of hydrochloric acid solution
Change behavior.And with the increase of Cr ingredient, Fe80-xCrxP13C7The corrosion potential of block alloyE corr Increase, corrosion current
DensityI corr Reduce, shows Fe80-xCrxP13C7The corrosion resistance of bulk amorphous alloy increases with the increase of Cr content.
The addition of Mo as shown in Figure 5 leads to Fe80P13C7The increase of bulk amorphous alloy corrosion resistance.When Mo ingredient increases to 7 from 0
When at.%, alloyE corr Increase,I corr Reduce, illustrates that its amorphous alloy corrosion resistance gradually increases.However when Mo ingredient is super
After crossing 7 at.% of addition, Fe80-xMoxP13C7Bulk amorphous alloyE corr Increase,I p It increases, and is passivated sector width and starts
Reduce, shows that corrosion resistance starts to reduce.The addition of Mo as shown in Figure 6 helps to inhibit bulk amorphous alloy
Fe65Cr5Mo10P13C7The active dissolution of Cr in active region illustrates that the synergistic effect of Cr and Mo are more advantageous to bulk amorphous alloy
The raising of corrosion resistance.
Claims (9)
1. a kind of iron-base block amorphous state alloy and preparation method thereof with high corrosion resistance, it is characterised in that obtained sample
Very high corrosion resistance, and realized by following below scheme: it accurately configures and is fused into master alloy first passing through in advance
Ingredient is Fe65Cr10Mo5P13C7Alloy is placed in quartz test tube together with oxide powder, is subsequently placed in high temperature furnace, alloy quilt
Oxide melt package is purified for a long time；After purification process, alloy is put into special quartz test tube, and will dress
The special quartz test tube for entering alloy sample is connected to mechanical pump and vacuumizes；It is located at special quartz test tube top rubble with firelock heating
The alloy at English test tube position, is allowed to melt, and alloy molten solution is located at the thick quartz test tube position in top of special quartz test tube at this time, closes
After golden melt sufficiently melts, argon gas is passed through into special quartz test tube；Punching press of the alloy molten solution by argon gas, entrance are special
The fine quartz test tube part of quartz test tube lower part, and alloy sample is heated using firelock, to ensure that alloy sample is in melting
Quartz test tube is rapidly inserted into water by state, and the molten alloy sample in quartz test tube lower part fine quartz test tube position is quick
It is cooling, to form rodlike Fe65Cr10Mo5P13C7Bulk amorphous alloy.
2. the method as described in claim 1, which is characterized in that Fe, Mo, Cr, Fe used3P, the purity of C element is not less than 98
wt.%。
3. the method as described in claim 1, which is characterized in that oxide used is anhydrous B2O3With CaO, mass ratio 3:1.
4. the method as described in claim 1, which is characterized in that special quartz test tube is by being with firelock calcination outer diameter
In the middle part of the common quartz test tube of 1 mm of 15mm/ wall thickness, after three four minutes, test tube starts to become soft, and test tube is moved away from flame,
Both hands lift two sections of test tube simultaneously, test tube cool down just become both ends outer diameter be still 15 mm quartz test tube, and middle part
The thin-walled fine quartz test tube of formation length about 80-100 mm, outer diameter about 2-5 mm, wall thickness about 0.1-0.3 mm, then from middle part
Quartz test tube is blown and sealed by firelock, (upper part is 15 mm/ wall thickness 1 of outer diameter to obtain required special quartz test tube
The thick quartz test tube of mm, and lower part is length about 50-100 mm, the thin-walled of outer diameter about 2-3 mm, wall thickness about 0.1-0.3 mm are thin
Quartz test tube, and tail portion is sealed).
5. the method as described in claim 1, which is characterized in that alloy is put into medium of oxides and purifies, and the purification time is extremely
Few 4 hours.
6. the method as described in claim 1, which is characterized in that quartz test tube keeps vacuum degree to be passed through argon gas after 50 Pa, so
It is evacuated again afterwards, keeps 50 Pa of vacuum degree, carries out scrubbing operations, this operation at least 3 times repeatedly.
7. the method as described in claim 1, which is characterized in that before heating alloy in special quartz test tube, should first be passed through
0.9×105The argon gas of Pa is passed through 1.5 × 10 after fusing5The argon gas of Pa.
8. the method as described in claim 1, which is characterized in that enter the melting of the fine acicular part of special quartz test tube front end
Alloy should keep the temperature 30 seconds to one minute before being quickly cooled down into the water in high temperature furnace.
9. the method as described in claim 1, which is characterized in that the measurement of the corrosion rate of gained sample is submerged by sample
Of poor quality before and after 168 hours in 1 mole of every liter of hydrochloric acid solution and obtain.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910158875.7A CN109930086A (en) | 2019-03-04 | 2019-03-04 | A kind of iron-base block amorphous state alloy and preparation method thereof with high corrosion resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910158875.7A CN109930086A (en) | 2019-03-04 | 2019-03-04 | A kind of iron-base block amorphous state alloy and preparation method thereof with high corrosion resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109930086A true CN109930086A (en) | 2019-06-25 |
Family
ID=66986178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910158875.7A Pending CN109930086A (en) | 2019-03-04 | 2019-03-04 | A kind of iron-base block amorphous state alloy and preparation method thereof with high corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109930086A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114075641A (en) * | 2020-08-21 | 2022-02-22 | 新疆大学 | Method for simultaneously improving iron-based amorphous strength and plasticity |
| CN115198209A (en) * | 2021-04-09 | 2022-10-18 | 泰州市新龙翔金属制品有限公司 | Iron-based alloy applied to tooth root implant and preparation process thereof |
| CN115652225A (en) * | 2022-11-03 | 2023-01-31 | 新疆大学 | Ni-based bulk amorphous alloy with room temperature large plasticity and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060213587A1 (en) * | 2003-06-02 | 2006-09-28 | Shiflet Gary J | Non-ferromagnetic amorphous steel alloys containing large-atom metals |
| JP2009270152A (en) * | 2008-05-07 | 2009-11-19 | Nakayama Steel Works Ltd | Highly corrosion-resistant amorphous alloy |
| CN102002650A (en) * | 2010-11-04 | 2011-04-06 | 新疆大学 | Quartz tube blowing method for preparing columnar block amorphous alloy |
| CN103805921A (en) * | 2014-01-24 | 2014-05-21 | 新疆大学 | Blow molding method for preparing columnar iron-based bulk amorphous alloy quartz tube by utilizing industrial grade raw materials |
| CN106435407A (en) * | 2016-09-30 | 2017-02-22 | 中国矿业大学 | Preparation method of dumbbell-shaped iron-based block metal glass sample |
| CN106906432A (en) * | 2017-04-19 | 2017-06-30 | 新疆大学 | A kind of cobalt-base body amorphous state alloy with nearly room temperature magnetothermal effect and preparation method thereof |
-
2019
- 2019-03-04 CN CN201910158875.7A patent/CN109930086A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060213587A1 (en) * | 2003-06-02 | 2006-09-28 | Shiflet Gary J | Non-ferromagnetic amorphous steel alloys containing large-atom metals |
| JP2009270152A (en) * | 2008-05-07 | 2009-11-19 | Nakayama Steel Works Ltd | Highly corrosion-resistant amorphous alloy |
| CN102002650A (en) * | 2010-11-04 | 2011-04-06 | 新疆大学 | Quartz tube blowing method for preparing columnar block amorphous alloy |
| CN103805921A (en) * | 2014-01-24 | 2014-05-21 | 新疆大学 | Blow molding method for preparing columnar iron-based bulk amorphous alloy quartz tube by utilizing industrial grade raw materials |
| CN106435407A (en) * | 2016-09-30 | 2017-02-22 | 中国矿业大学 | Preparation method of dumbbell-shaped iron-based block metal glass sample |
| CN106906432A (en) * | 2017-04-19 | 2017-06-30 | 新疆大学 | A kind of cobalt-base body amorphous state alloy with nearly room temperature magnetothermal effect and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 马村成 等: ""FeMoCrPC非晶态合金的制备及其性能研究"", 《铸造技术》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114075641A (en) * | 2020-08-21 | 2022-02-22 | 新疆大学 | Method for simultaneously improving iron-based amorphous strength and plasticity |
| CN115198209A (en) * | 2021-04-09 | 2022-10-18 | 泰州市新龙翔金属制品有限公司 | Iron-based alloy applied to tooth root implant and preparation process thereof |
| CN115652225A (en) * | 2022-11-03 | 2023-01-31 | 新疆大学 | Ni-based bulk amorphous alloy with room temperature large plasticity and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109930086A (en) | A kind of iron-base block amorphous state alloy and preparation method thereof with high corrosion resistance | |
| Lu et al. | Role of yttrium in glass formation of Fe-based bulk metallic glasses | |
| ES2388481T3 (en) | Hot work tool steel with extraordinary toughness and thermal conductivity | |
| CN100457955C (en) | Ferrum-base block non-crystalline alloy material | |
| Pang et al. | Formation of bulk glassy Fe75–x–yCrxMoyC15B10 alloys and their corrosion behavior | |
| CN106086715B (en) | A kind of all-metal element of Fe-Co-Ni-Mo-Hf non-crystaline amorphous metals and preparation method thereof | |
| CN101713055A (en) | Mg-Ni-Gd-Ag serial block amorphous alloy and preparation method thereof | |
| CN109321786A (en) | A kind of cobalt base superalloy and preparation method thereof | |
| CN103938132B (en) | A kind of zirconium-base amorphous alloy with strong glass forming ability | |
| CN107236913A (en) | A kind of zirconium-base amorphous alloy and preparation method thereof | |
| CN110106454A (en) | A kind of boryl amorphous alloy and preparation method thereof | |
| CN103805921B (en) | A kind of quartz tube blowing casting method utilizing industrial raw material to prepare the iron-base block amorphous state alloy of column | |
| Chen et al. | Role of rare-earth elements in glass formation of Al–Ca–Ni amorphous alloys | |
| CN109355601B (en) | Cobalt-based bulk amorphous alloy and preparation method thereof | |
| CN106906432A (en) | A kind of cobalt-base body amorphous state alloy with nearly room temperature magnetothermal effect and preparation method thereof | |
| Ming et al. | Nonequilibrium solidification and microstructures of metal phases in the shock‐induced melt of the Yanzhuang (H6) chondrite | |
| CN103757450A (en) | Preparation method of iron-based bulk amorphous alloy with high saturation magnetization | |
| CN106435407B (en) | Preparation method of dumbbell-shaped iron-based block metal glass sample | |
| CN106636979B (en) | A kind of Cr Fe Ni base block amorphous alloys with excellent corrosion resistance energy and preparation method thereof | |
| CN100356603C (en) | Novel rareearth super magnetostrictive material and preparation method thereof | |
| CN104046929B (en) | Cerium gallium base noncrystal alloy prepared by a kind of low-purity raw material cerium | |
| Doi et al. | Thermodynamic study of the phase equilibria in the Sn-Ag-Bi-Cu quaternary system | |
| Mizumoto et al. | Development of new additive for grain refinement of austenitic stainless steel | |
| CN110257734A (en) | Corrosion resistant iron-base amorphous alloy material and its preparation method and application | |
| CN109609880A (en) | A kind of light rare earth base block amorphous alloy and preparation method thereof containing metalloid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190625 |