CN109182961A - A kind of workpiece surface reinforcing low-temperature solid B-Cr-Re reducing agent - Google Patents
A kind of workpiece surface reinforcing low-temperature solid B-Cr-Re reducing agent Download PDFInfo
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- CN109182961A CN109182961A CN201811271740.3A CN201811271740A CN109182961A CN 109182961 A CN109182961 A CN 109182961A CN 201811271740 A CN201811271740 A CN 201811271740A CN 109182961 A CN109182961 A CN 109182961A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C12/00—Solid state diffusion of at least one non-metal element other than silicon and at least one metal element or silicon into metallic material surfaces
- C23C12/02—Diffusion in one step
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Abstract
The invention discloses a kind of workpiece surfaces to strengthen low-temperature solid B-Cr-Re reducing agent, calcium-silicon (CaSi2+ CaSi) 27.2-31.6 parts, aluminum oxide (Al2O3) 42.8-45.1 parts, 24.5-27.0 parts of magnesia (MgO).The invention has the following advantages that 1, permeation temperature is lower, cost is lower, workpiece deformation it is smaller, without phase-change, internal stress free, the application widened on precision part；2, low temperature co-penetration layer is finer and close, no hole, and thickness is about 23 ~ 44 μm, and application field is wider；3, low temperature co-penetration layer better quality, economy is more preferable, and industrialization potential is bigger.
Description
Technical field
The present invention relates to a kind of low-temperature reduction agent, specifically a kind of workpiece surface strengthens low-temperature solid B-Cr-Re also
Former agent.
Background technique
Workpiece surface can obtain certain thickness boride layer after Bononizing pretreatment, on surface, because boride layer have high rigidity,
The features such as high corrosion-resistant, high-wearing feature and excellent high temperature oxidation resistance, boronizing technology is made to obtain very extensive application, mesh
Before, it is mainly used in the reinforcing of the workpiece surfaces such as mining machinery, engineering machinery, agricultural tool.
Currently, boronizing method mainly includes gas boriding, liquid boriding and pack boriding.Wherein, gas boriding and liquid
Boronising limits its application because of technological deficiency significantly.The boronizing technology that domestic and foreign scholars mainly study is pack boriding, boronising temperature
About 750 DEG C -950 DEG C, the boronising time is about 1h-14h.The colleges and universities mainly studied of the country have Shandong University, the National University of Defense technology,
Wuhan University Of Technology, Jiamusi University, Shandong Agricultural University, Shandong University Building.But boronizing technology is deposited under process conditions in this way
Clearly disadvantageous: 1. boronising temperature is high, the time is long, it is larger to deform after heat treatment of workpieces；2. brittlement of boriding layer is big, with matrix knot
It closes loosely, is easy to peel off；It is the extensive use for further widening boriding process in view of the above deficiency.Domestic and foreign scholars, expert by
Step starts to explore the research of low-temperature boriding technology, and starts to try out in part workpiece surface.
So-called low-temperature boriding refers to carries out boronising below phase transition temperature.Since low-temperature boriding technology is available single-phase
Fe2B structure, therefore low-temperature boriding technology not only can reduce workpiece deformation；More it is reduction of boronising brittleness.This boronising skill
Art is especially suitable for some workpiece surfaces that structure is complicated, type chamber is small, required precision is high；The low-temperature boriding technique also has simultaneously
Simply, general, easy to operate, seep part easy cleaning the advantages that, it has also become boronizing technology development important component.To improve boron
Diffusion velocity when atom low temperature improves the quality of boride layer.Currently, Shandong University Building's Materials Academy Surface Science technical course
Topic group has gradually carried out a large amount of research work in the optimization of reducing agent component content, and effect is more obvious.Mainly using Si,
Ca, Al, Mg and its alloy etc. are reducing agent.
Chinese patent ZL200810015959.7 discloses a kind of pack chrome-RE-boronizing agent and its eutectoid line is below low
Warm co-penetration technology, wherein reducing agent is calcium-silicon in diffusion medium ingredient, and weight ratio is 11.0-11.5 parts, and permeation temperature is 680
DEG C, keep the temperature 4h.Workpiece obtains relatively single Fe after above-mentioned technique permeation is cooling2B structure, but co-penetration layer is shallower, co-penetration layer
On there are the holes of some size unevenness.
Chinese patent ZL201310297958.7 discloses a kind of novel boron-chromium-low-temperature rare diffusion medium, wherein permeation
Reducing agent is aluminum oxide in agent ingredient, and weight ratio is 21.3-24.5 parts, and permeation temperature is 600 DEG C and 650 DEG C, keeps the temperature 6h.
The dosage of a relatively upper patent energizer is substantially reduced, and workpiece is still single-phase Fe after this technique permeation is cooling2B structure,
Co-penetration layer thickness is about 30-52 μm.But the hole that size unevenness is still had on co-penetration layer, influences answering on accurate device
With.
Summary of the invention
The purpose of the present invention is to overcome above-mentioned the deficiencies in the prior art, provide a kind of infiltration front surface quenching treatment low-temperature solid
Body B-Cr-Re be total to osmosis work-piece deformation it is small, without phase-change, internal stress free, co-penetration layer it is finer and close, without hole, cost is lower, technology
Industrialization potential is bigger, while obtaining single-phase Fe2The low-temperature solid B-Cr-Re permeation reducing agent of B structure co-penetration layer.
To achieve the above object, the present invention adopts the following technical solutions:
A kind of workpiece surface reinforcing low-temperature solid B-Cr-Re reducing agent, component content in mass ratio are as follows: calcium-silicon (CaSi2
+ CaSi) 27.2-31.6 parts, aluminum oxide (Al2O3) 42.8-45.1 parts, 24.5-27.0 parts of magnesia (MgO).
A kind of workpiece surface reinforcing low-temperature solid B-Cr-Re reducing agent, component content in mass ratio are as follows: calcium-silicon
(CaSi2+ CaSi) 27.2 parts, aluminum oxide (Al2O3) 42.8 parts, 24.5 parts of magnesia (MgO).
A kind of workpiece surface reinforcing low-temperature solid B-Cr-Re reducing agent, component content in mass ratio are as follows: calcium-silicon
(CaSi2+ CaSi) 29.5 parts, aluminum oxide (Al2O3) 43.9 parts, 26.6 parts of magnesia (MgO).
A kind of workpiece surface reinforcing low-temperature solid B-Cr-Re reducing agent, component content in mass ratio are as follows: calcium-silicon
(CaSi2+ CaSi) 28.4 parts, aluminum oxide (Al2O3) 44.8 parts, 26.8 parts of magnesia (MgO).
A kind of workpiece surface reinforcing low-temperature solid B-Cr-Re reducing agent, component content in mass ratio are as follows: calcium-silicon
(CaSi2+ CaSi) 31.6 parts, aluminum oxide (Al2O3) 45.1 parts, 27.0 parts of magnesia (MgO).
Using the diffusion medium co-penetration technology of the reducing agent, including workpiece seeps front surface quenching treatment, reducing agent is prepared, reduction
Agent stir process, diffusion medium are prepared, workpiece is cased, low temperature B-Cr-Re permeation step.
Low-temperature solid B-Cr-Re reducing agent improves co-penetration layer compactness and eliminates the Analysis on Mechanism of hole
To widen application of the carbon steel on accurate device, using the more first low temperature permeations of B-Cr-Re, but traditional handicraft infiltration rate it is lower,
Infiltration layer is shallower.To improve infiltration rate, using carbon steel surface hardening processing before seeping, through surface hardening treated carbon steel surface layer there is
Fault of construction, such as: martensite and retained austenite, residual stress etc..These defects can be the more members of subsequent B-Cr-Re
Permeation provides structural condition and energy condition, improves the thickness of co-penetration layer, improves the quality of co-penetration layer.
The B-Cr-Re low temperature permeation of carbon steel surface depends on the function and effect of boronising when reducing agent is compound type reducing agent
In the result of whole diffusion medium component interaction.For the application for further increasing B-Cr-Re low temperature permeation technology, meet production
It needs, through a large number of experiments studies have shown that reducing agent is calcium-silicon (CaSi2+ CaSi), aluminum oxide (Al2O3), oxygen
When changing magnesium (MgO), permeation effect is far superior to the reducing agent of single-phase ingredient.
Reducing agent at high temperature, respectively with BF3And B2O3It reacts, generates a large amount of active boron atoms；At the same time,
It reacts with rare earth compound, generates a large amount of active rare earth atoms.This plays actively the B-Cr-Re low temperature permeation in later period
Effect, improve the compactness of co-penetration layer.It chemically reacts as follows:
4BF3+3M→3MF4+4[B]
B2O3+3M→3MO+2[B]
2LaCl3 (s)+3M→2[La]+3MCl2
2CeCl3(s)+3M→2[Ce]+3MCl2
The phase composition of industrial calcium-silicon is CaSi2About 77%, CaSi about 5%-15%, Si < 20%, SiC < 8%, density is about
For 2.2g/cm3, fusion temperature range is 980-1200 DEG C.Calcium-silicon is while diffusion medium component reacts to each other, actively also
Original goes out a large amount of active boron atoms and rare earth atom, promotes the progress of permeation process；Calcium-silicon can also play purification simultaneously
The effect of co-penetration layer, reducing impurity influences co-penetration layer, increases the compactness of co-penetration layer.
Commercial alumina is insoluble in the white solid of water, odorless, tasteless.Density is about 3.97 g/cm3, 2030 DEG C of fusing point,
2977 DEG C of boiling point.It is being played except reduction, also acts as suction-operated, and reducing impurity influences co-penetration layer, increases permeation
The compactness of layer.
Magnesia is odorless, tasteless, nontoxic, is typical alkaline earth oxide, and 2852 DEG C of fusing point, 3600 DEG C of boiling point, phase
It is 3.58 g/cm to density3(25 DEG C).
Interaction between compound type reducing agent and the other components of diffusion medium, inspires more active atomics, not only
Actively promote the speed of permeation；Influence of the impurity to co-penetration layer is also reduced, the compactness of co-penetration layer is effectively improved.
The invention has the following advantages that
1, permeation temperature is lower, and cost is lower, workpiece deformation it is smaller, without phase-change, internal stress free, widened answering on precision part
With.
2, low temperature co-penetration layer is finer and close, no hole, and thickness is about 23 ~ 44 μm, and application field is wider.
3, low temperature co-penetration layer better quality, economy is more preferable, and industrialization potential is bigger.
Detailed description of the invention
Fig. 1 is the organizational topography through 580 DEG C × 5h co-penetration layer after Q235 steel surface quenching treatment；
Fig. 2 is the organizational topography through 590 DEG C × 5h co-penetration layer after Q235 steel surface quenching treatment；
Fig. 3 is the organizational topography through 580 DEG C × 5h co-penetration layer after 45 steel surfaces quenching treatment；
Fig. 4 is the organizational topography through 590 DEG C × 5h co-penetration layer after 45 steel surfaces quenching treatment.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and examples.
Embodiment 1: a kind of workpiece surface reinforcing low-temperature solid B-Cr-Re reducing agent, component content in mass ratio are as follows: silicon
Calcium alloy (CaSi2+ CaSi) 27.2 parts, aluminum oxide (Al2O3) 42.8 parts, 24.5 parts of magnesia (MgO).
Q235 steel curved beam is carried out to seep front surface quenching treatment, surface hardening processing parameter are as follows: when 940 DEG C of temperature, heat preservation
Between 14S, water quenching, B-Cr-Re permeation is then carried out under the conditions of 580 DEG C × 5h, sample is observed after infiltration.Its technical process
It is as follows:
1. pair workpiece carries out seeping front surface quenching treatment
Surface hardening processing parameter are as follows: 940 DEG C of temperature, soaking time 14S, water quenching.
2. reducing agent is prepared
It is prepared according to aforementioned proportion, specific process for preparation is as follows:
A. by calcium-silicon (CaSi2+ CaSi), aluminum oxide (Al2O3), magnesia (MgO) matched according to aforementioned proportion
It makes, and all components is ground into the particle of 100 mesh or so, stir evenly simultaneously；
B. it further crushes, while stirring evenly simultaneously；
3. diffusion medium is prepared
It is prepared according to the ratio of diffusion medium, specific process for preparation is as follows:
A. preparation reducing agent is carried out according to aforementioned proportion, and be constantly stirred；
B., other materials in diffusion medium are ground into the particle of 100 mesh or so, and are sufficiently stirred with reducing agent component each in a
It mixes；
C. by the diffusion medium b stirred evenly 180 DEG C drying 2-3 hours, furnace is cold；
D. the diffusion medium c after drying is further crushed, then be stirred, caused uniform；
E. the diffusion medium d stirred evenly is placed in dry container, for use.
4. vanning
By prepared diffusion medium, case according to the principle of workpiece after first penetration enhancer；And guarantee between workpiece and workpiece, workpiece
It should be kept at a distance from 40-50mm between chamber wall.
5.B-Cr-Re permeation
After vanning finishes, it is sealed with double-deck waterglass+clay, is placed 24 hours in dry environment；Heating furnace heating
To 580 DEG C, case will be seeped and be put into, timing keeps the temperature 5 hours, and furnace is cold.
As shown in Figure 1, B-Cr-Re permeation of the Q235 steel through 580 DEG C × 5h, co-penetration layer dense structure, without hole, more
It is even, with a thickness of 32 μm -39 μm, co-penetration layer is high-quality.
Embodiment 2: a kind of workpiece surface reinforcing low-temperature solid B-Cr-Re reducing agent, component content in mass ratio are as follows: silicon
Calcium alloy (CaSi2+ CaSi) 29.5 parts, aluminum oxide (Al2O3) 43.9 parts, 26.6 parts of magnesia (MgO).
Q235 steel curved beam is carried out to seep front surface quenching treatment, surface hardening processing parameter are as follows: when 940 DEG C of temperature, heat preservation
Between 14S, water quenching, B-Cr-Re permeation is then carried out under the conditions of 590 DEG C × 5h, sample is observed after infiltration.Its technical process
It is as follows:
1. pair workpiece carries out seeping front surface quenching treatment
Surface hardening processing parameter are as follows: 940 DEG C of temperature, soaking time 14S, water quenching.
2. reducing agent is prepared
It is prepared according to aforementioned proportion, specific process for preparation is as follows:
A. by calcium-silicon (CaSi2+ CaSi), aluminum oxide (Al2O3), magnesia (MgO) matched according to aforementioned proportion
It makes, and all components is ground into the particle of 100 mesh or so, stir evenly simultaneously；
B. it further crushes, while stirring evenly simultaneously；
3. diffusion medium is prepared
It is prepared according to the ratio of diffusion medium, specific process for preparation is as follows:
A. preparation reducing agent is carried out according to aforementioned proportion, and be constantly stirred；
B., other materials in diffusion medium are ground into the particle of 100 mesh or so, and are sufficiently stirred with reducing agent component each in a
It mixes；
C. by the diffusion medium b stirred evenly 180 DEG C drying 2-3 hours, furnace is cold；
D. the diffusion medium c after drying is further crushed, then be stirred, caused uniform；
E. the diffusion medium d stirred evenly is placed in dry container, for use.
4. vanning
By prepared diffusion medium, case according to the principle of workpiece after first penetration enhancer；And guarantee between workpiece and workpiece, workpiece
It should be kept at a distance from 40-50mm between chamber wall.
5.B-Cr-Re permeation
After vanning finishes, it is sealed with double-deck waterglass+clay, is placed 24 hours in dry environment；Heating furnace heating
To 590 DEG C, case will be seeped and be put into, timing keeps the temperature 5 hours, and furnace is cold.
As shown in Fig. 2, B-Cr-Re permeation of the Q235 steel through 590 DEG C × 5h, co-penetration layer dense structure, without hole, more
It is even, with a thickness of 36 μm -43 μm, co-penetration layer is high-quality.
Embodiment 3: a kind of workpiece surface reinforcing low-temperature solid B-Cr-Re reducing agent, component content in mass ratio are as follows: silicon
Calcium alloy (CaSi2+ CaSi) 28.4 parts, aluminum oxide (Al2O3) 44.8 parts, 26.8 parts of magnesia (MgO).
45 steel curved beams are carried out to seep front surface quenching treatment, surface hardening processing parameter are as follows: 860 DEG C of temperature, soaking time
Then 14S, water quenching carry out B-Cr-Re permeation under the conditions of 580 DEG C × 5h, observe after infiltration sample.Its technical process is such as
Under:
1. pair workpiece carries out seeping front surface quenching treatment
Surface hardening processing parameter are as follows: 860 DEG C of temperature, soaking time 14S, water quenching.
2. reducing agent is prepared
It is prepared according to aforementioned proportion, specific process for preparation is as follows:
A. by calcium-silicon (CaSi2+ CaSi), aluminum oxide (Al2O3), magnesia (MgO) matched according to aforementioned proportion
It makes, and all components is ground into the particle of 100 mesh or so, stir evenly simultaneously；
B. it further crushes, while stirring evenly simultaneously；
3. diffusion medium is prepared
It is prepared according to the ratio of diffusion medium, specific process for preparation is as follows:
A. preparation reducing agent is carried out according to aforementioned proportion, and be constantly stirred；
B., other materials in diffusion medium are ground into the particle of 100 mesh or so, and are sufficiently stirred with reducing agent component each in a
It mixes；
C. by the diffusion medium b stirred evenly 180 DEG C drying 2-3 hours, furnace is cold；
D. the diffusion medium c after drying is further crushed, then be stirred, caused uniform；
E. the diffusion medium d stirred evenly is placed in dry container, for use.
4. vanning
By prepared diffusion medium, case according to the principle of workpiece after first penetration enhancer；And guarantee between workpiece and workpiece, workpiece
It should be kept at a distance from 40-50mm between chamber wall.
5.B-Cr-Re permeation
After vanning finishes, it is sealed with double-deck waterglass+clay, is placed 24 hours in dry environment；Heating furnace heating
To 580 DEG C, case will be seeped and be put into, timing keeps the temperature 5 hours, and furnace is cold.
As shown in figure 3, B-Cr-Re permeation of 45 steel through 580 DEG C × 5h, co-penetration layer dense structure, without hole, dentation shape
Looks, more uniformly, with a thickness of 23 μm -28 μm, co-penetration layer is high-quality.
Embodiment 4: a kind of workpiece surface reinforcing low-temperature solid B-Cr-Re reducing agent, component content in mass ratio are as follows: silicon
Calcium alloy (CaSi2+ CaSi) 31.6 parts, aluminum oxide (Al2O3) 45.1 parts, 27.0 parts of magnesia (MgO).
45 steel curved beams are carried out to seep front surface quenching treatment, surface hardening processing parameter are as follows: 860 DEG C of temperature, soaking time
Then 14S, water quenching carry out B-Cr-Re permeation under the conditions of 590 DEG C × 5h, observe after infiltration sample.Its technical process is such as
Under:
1. pair workpiece carries out seeping front surface quenching treatment
Surface hardening processing parameter are as follows: 860 DEG C of temperature, soaking time 14S, water quenching.
2. reducing agent is prepared
It is prepared according to aforementioned proportion, specific process for preparation is as follows:
A. by calcium-silicon (CaSi2+ CaSi), aluminum oxide (Al2O3), magnesia (MgO) matched according to aforementioned proportion
It makes, and all components is ground into the particle of 100 mesh or so, stir evenly simultaneously；
B. it further crushes, while stirring evenly simultaneously；
3. diffusion medium is prepared
It is prepared according to the ratio of diffusion medium, specific process for preparation is as follows:
A. preparation reducing agent is carried out according to aforementioned proportion, and be constantly stirred；
B., other materials in diffusion medium are ground into the particle of 100 mesh or so, and are sufficiently stirred with reducing agent component each in a
It mixes；
C. by the diffusion medium b stirred evenly 180 DEG C drying 2-3 hours, furnace is cold；
D. the diffusion medium c after drying is further crushed, then be stirred, caused uniform；
E. the diffusion medium d stirred evenly is placed in dry container, for use.
4. vanning
By prepared diffusion medium, case according to the principle of workpiece after first penetration enhancer；And guarantee between workpiece and workpiece, workpiece
It should be kept at a distance from 40-50mm between chamber wall.
5.B-Cr-Re permeation
After vanning finishes, it is sealed with double-deck waterglass+clay, is placed 24 hours in dry environment；Heating furnace heating
To 590 DEG C, case will be seeped and be put into, timing keeps the temperature 5 hours, and furnace is cold.
As shown in figure 4, B-Cr-Re permeation of 45 steel through 590 DEG C × 5h, co-penetration layer dense structure, without hole, dentation shape
Looks, more uniformly, with a thickness of 23 μm -30 μm, co-penetration layer is high-quality.
Claims (5)
1. a kind of workpiece surface strengthens low-temperature solid B-Cr-Re reducing agent, component content in mass ratio are as follows: calcium-silicon
(CaSi2+ CaSi) 27.2-31.6 parts, aluminum oxide (Al2O3) 42.8-45.1 parts, 24.5-27.0 parts of magnesia (MgO).
2. a kind of workpiece surface strengthens low-temperature solid B-Cr-Re reducing agent, component content in mass ratio are as follows: calcium-silicon
(CaSi2+ CaSi) 27.2 parts, aluminum oxide (Al2O3) 42.8 parts, 24.5 parts of magnesia (MgO).
3. a kind of workpiece surface strengthens low-temperature solid B-Cr-Re reducing agent, component content in mass ratio are as follows: calcium-silicon
(CaSi2+ CaSi) 29.5 parts, aluminum oxide (Al2O3) 43.9 parts, 26.6 parts of magnesia (MgO).
4. a kind of workpiece surface strengthens low-temperature solid B-Cr-Re reducing agent, component content in mass ratio are as follows: calcium-silicon
(CaSi2+ CaSi) 28.4 parts, aluminum oxide (Al2O3) 44.8 parts, 26.8 parts of magnesia (MgO).
5. a kind of workpiece surface strengthens low-temperature solid B-Cr-Re reducing agent, component content in mass ratio are as follows: calcium-silicon
(CaSi2+ CaSi) 31.6 parts, aluminum oxide (Al2O3) 45.1 parts, 27.0 parts of magnesia (MgO).
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| US20130269837A1 (en) * | 2012-04-17 | 2013-10-17 | Lidiya Omovna CHUNYAYEVA | Composition and method for diffusion alloying of ferrocarbon workpiece |
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| CN103343314A (en) * | 2013-07-06 | 2013-10-09 | 许斌 | Novel low-temperature rare earth-chromium-boronizing agent |
| CN103882372A (en) * | 2014-04-01 | 2014-06-25 | 山东建筑大学 | New surface strengthening method for medium and low carbon steels |
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Application publication date: 20190111 |