CN104388717A - Method for quickly preparing gradient cemented carbide by adding rare-earth elements - Google Patents
Method for quickly preparing gradient cemented carbide by adding rare-earth elements Download PDFInfo
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- CN104388717A CN104388717A CN201410779674.6A CN201410779674A CN104388717A CN 104388717 A CN104388717 A CN 104388717A CN 201410779674 A CN201410779674 A CN 201410779674A CN 104388717 A CN104388717 A CN 104388717A
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Abstract
The invention discloses a method for quickly preparing gradient cemented carbide by adding rare-earth elements, and belongs to the field of manufacturing cemented carbide materials. The method disclosed by the invention comprises the following steps: pressing and forming carbon-poor cemented carbide powder containing rare earth, and performing vacuum sintering to obtain a carbon-poor presintering base body; performing carburizing treatment for 40-120 minutes at the temperature of 1,400-1,460 DEG C under the hydrogen atmosphere to obtain the gradient cemented carbide, wherein the thickness of a gradient layer of the gradient cemented carbide is 200-3000 [mu]m. The rare-earth elements are added in the process of preparing the gradient cemented carbide, so that alloying components are solidified and dissolved in a Co phase in the presintering process, and the effect of inhibiting crystal grains from growing can be achieved. But in the carburizing process, the influence of adding the rare earth on the dissolution and the separation of WC (wolfram carbide) in the Co phase is weakened, and more passages are provided for the diffusion of activated carbon, so that the thickness of the gradient layer of the alloy can be quickly increased.
Description
Technical field
The invention discloses a kind of method of adding rare earth element and preparing gradient hard alloy fast, belong to Hardmetal materials and manufacture field.
Background technology
Wimet be a kind of with refractory metal compound (WC, TaC, TiC, NbC etc.) for matrix, with transition group metal (Co, Ni, Fe) for Binder Phase, adopt composite tool material prepared by powder metallurgy process.Due to its high strength, high rigidity, high elastic coefficient, the advantage such as wear-resistant, corrosion-resistant, in metal cutting, wood working, mine probing etc., there is important effect.Usually, hardness and the wear resistance of carbide alloy play an important role, and the obdurability of Binder Phase alloy produces material impact.In general, increase WC grain size or increase Co content, the Binder Phase thickness of alloy can increase, and the plasticity of alloy also can be improved.But after plasticity improves, alloy local stress easily relaxes because of deformation; The alloy of plasticity difference, stress relaxes and causes the initiation and propogation of crackle, causes alloy to break.So traditional method to carry heavy alloyed Co content and to increase WC grain size as the direction of improving Wimet toughness.But hardness and wear resistance can be made again to decline so simultaneously; Otherwise hardness and wear resistance can improve, but intensity and toughness decline.Therefore there is sharp-pointed contradiction in the hardness of Wimet and toughness, is difficult to allow the hardness of alloy and toughness improve in traditional homogeneous Wimet simultaneously.
In order to overcome this problem, last century the eighties, Sandvik company of Sweden have developed gradient hard alloy, and this kind of alloy outer Co content, lower than the nominal content of alloy, has very high hardness and wear resisting property; Middle layer Co content, higher than the nominal composition of alloy, has good toughness and intensity.The patent CN102031435A that this study group announces simultaneously is disclosed a kind of Wimet changed in gradient by carburizing acquisition top layer Co content and prepares technique, by decarburized alloy is carried out carburizing treatment in a hydrogen atmosphere, namely obtains gradient hard alloy.
But in cementation process, alloy surface easily occurs Phenomena of Grain Growth, so a lot of research concentrates on the grain growth adding to suppress alloy of grain inhibitor.Add rare earth and have obvious effect to Wimet crystal grain thinning, patent CN101760685A effectively inhibits grain growth by the mode adding rare earth oxide or Co-RE composite powder and add, obtain ultra-fine cemented carbide, but this patent does not relate to and prepares the controlled gradient hard alloy of gradient layer how fast.Patent CN102672184A discloses a kind of by adding nano rare earth surface strengthening gradient hard alloy, puies forward heavy alloyed over-all properties.This patent does not relate to yet how fast prepares the controlled gradient hard alloy of gradient layer.
In gradient hard alloy research, concrete technology research is more, but to gradient hard alloy gauge control and how prepare the Wimet with gradient layer fast and also do not specialize in.Nearest research finds that the content of decarburization phase and distribution thereof are formed with considerable influence to gradient, it is generally acknowledged that the volume fraction of decarburization phase is between 5%-35%, are conducive to obtaining good gradient-structure in follow-up cementation process; The intensity of Thickness of Gradient Layer alloy plays an important role.In addition, the research adding alloy group member in graded alloy is also little.
Summary of the invention
The present invention is directed to the existing deficiency preparing gradient hard alloy, a kind of method of adding rare earth element and preparing gradient hard alloy is fast provided.
A kind of method of adding rare earth element and preparing gradient hard alloy fast of the present invention, comprises the steps:
Step one
By containing after the poor carbon cemented carbide powder press forming of rare earth, vacuum sintering, obtains poor carbon presintering matrix; Described rare earth is rare earth metal; Described poor carbon cemented carbide powder comprises by percentage to the quality:
WC 78 ~ 88%; Be preferably 82-88%; More preferably 84-86%;
Co 5.5 ~ 12%; Be preferably 5.5-10%; More preferably 6-8%;
Rare earth element 0.3-1.2%; Be preferably 0.5-1.0%; More preferably 0.5-0.7%;
W simple substance 5-12%; Be preferably 5-10%; More preferably 6-8%;
Step 2
Poor for step one gained carbon presintering matrix is placed in hydrogen atmosphere, carries out carburizing treatment 40 ~ 120 minutes at 1400 ~ 1460 DEG C, be preferably 40-100 minute, more preferably 40-80 minute, obtain gradient hard alloy.
A kind of method of adding rare earth element and preparing gradient hard alloy fast of the present invention, the rare earth element in poor carbon cemented carbide powder is preferably rare earth metal.
A kind of method of adding rare earth element and preparing gradient hard alloy fast of the present invention, the described poor carbon cemented carbide powder containing rare earth is prepared by following proposal:
Component by design is joined after WC powder, Co powder, W powder, the rareearth oxidate powder got mix, be reduced to rare earth oxide in a hydrogen atmosphere and be converted into rare earth metal completely, then obtain through wet-milling, drying, granulation the poor carbon cemented carbide powder containing rare earth that granularity is 1.5-3.0 μm.
A kind of method of adding rare earth element and preparing gradient hard alloy fast of the present invention, the granularity of described WC powder is 2.0 ~ 5.0 μm; The granularity of described Co powder is 1.5-3.5 μm; The granularity of described W powder is 1.8-3.5 μm; The granularity of described rareearth oxidate powder is 1.5-3.0 μm.
A kind of method of adding rare earth element and preparing gradient hard alloy fast of the present invention, described rare earth oxide is selected from Y
2o
3, La
2o
3, CeO
2in at least one.
A kind of method of adding rare earth element and preparing gradient hard alloy fast of the present invention, is joined WC powder, Co powder, W powder, the rareearth oxidate powder got and is mixed by dry type ball milling by the component by design.
A kind of method of adding rare earth element and preparing gradient hard alloy fast of the present invention, component by design is joined after WC powder, Co powder, W powder, the rareearth oxidate powder got mix, reduce in hydrogen atmosphere, the temperature of reduction is 850 ~ 1100 DEG C, the time is 30 ~ 60 minutes;
Reduction reaction equation is:
Y
2O
3+3H
2＝2Y+3H
2O；
La
2O
3+3H
2＝2La+3H
2O；
CeO
2+2H
2＝Ce+2H
2O。
A kind of method of adding rare earth element and preparing gradient hard alloy fast of the present invention, by the poor carbon cemented carbide powder containing rare earth after press forming under 100-300MPa, through pressure sintering, obtains poor carbon presintering matrix; During pressure sintering, control temperature is 1420 ~ 1450 DEG C, vacuum tightness is 6 × 10
-3~ 5 × 10
-4pa, pressure is 4 ~ 6MPa, and the time is 40 ~ 90min.
In actual mechanical process, before press forming, the poor carbon cemented carbide powder containing rare earth need be mixed with caking agent; Required caking agent is the caking agent that Wimet prepares often, is preferably paraffin.Therefore need first to carry out dewaxing treatment after press forming, then carry out pressure sintering; The condition of described dewaxing treatment is: in vacuum degreasing stove, is heated to 170-190 DEG C of insulation 30-50min, is then warming up to 410-430 DEG C, and is incubated 20-50min.The caking agent of object mainly in order to introduce during Material removal of dewaxing.
A kind of method of adding rare earth element and preparing gradient hard alloy fast of the present invention, in step 2, carburizing carbon source used is selected from least one in compact crystal shape graphite, flaky graphite, aphanitic graphite, is preferably solid flaky graphite.
A kind of method of adding rare earth element and preparing gradient hard alloy fast of the present invention, in step 2, when carburizing temperature is 1420 DEG C, after 40min carburizing, the thickness of gained gradient layer can reach 802 μm; And the Wimet gained gradient layer not adding rare earth metal is only 680 μm.
A kind of method of adding rare earth element and preparing gradient hard alloy fast of the present invention, in step 2, after 80min carburizing, the thickness of gained gradient layer can reach 2751 μm, and the Wimet gained gradient layer not adding rare earth metal is only 1685 μm; The average one-tenth speed of gradient layer of the present invention in 80min is 1.65 times that do not add carbide alloy of rare earth under equal conditions it can be seen.
A kind of method of adding rare earth element and preparing gradient hard alloy fast of the present invention, the thickness of gained gradient layer is controlled, can obtain by control carburizing temperature and carburizing time the gradient layer that thickness is 200 ~ 3000 μm.
A kind of method of adding rare earth element and preparing gradient hard alloy fast of the present invention, the surface hardness of gained Wimet is more than or equal to 91HRA.
A kind of method of adding rare earth element and preparing gradient hard alloy fast of the present invention, the bending strength of gained Wimet is more than or equal to 2000MPa; Reach as high as 2500MPa.
A kind of method of adding rare earth element and preparing gradient hard alloy fast of the present invention, after obtained gradient hard alloy, detects graded alloy thickness; Detecting graded alloy thickness approach is:
First alloy surface is polished, polishing, under scanning electronic microscope (SEM), take BSE pattern, observe alloy surface Thickness of Gradient Layer under low power, SEM photo calculates its Thickness of Gradient Layer under Image Pro Plus software, averages.
Beneficial effect
The present invention, owing to the addition of rare earth oxide preparing in gradient hard alloy process, is reduced to rare earth metal after mixing.In the sintering process of step one, rare earth element can be solidly soluted in Co phase on the one hand, reduces the solution modeling of WC in Co, plays the effect of inhibiting grain growth; On the other hand, because rare earth element is more active relative to other element in Wimet, the impurity such as oxygen, sulphur easily in alloy is combined, and purification crystal boundary, eliminates defect.In the cementation process of step 2, rare earth can slow down the solution modeling of WC in Co phase, and then greatly slow down growing up of WC grain, and this provides prerequisite for preparing high-performance carbide; Simultaneously owing to slow down growing up of WC grain, this just provides more passage for active Carbon diffusion, and this makes to obtain at 40 ~ 120 minutes thickness is that the gradient layer of 200 ~ 3000 μm becomes feasible.Simultaneously owing to shortening carburizing time, under the synergy of rare earth element, the particle diameter of WC in the Wimet making the grain-size separating out WC be far smaller than prepared by prior art.
The present invention, in the cementation process of step 2, lacks carbon phase (W
3co
3c or W
6co
6c) react with gac, produce more WC and Co, in the Co phase of top layer, the rare earth element of solid solution is along with Co internal migration in opposite directions, and this provides prerequisite for preparing gradient hard alloy material.Rare earth element slow down the solution modeling of alloy simultaneously; This provides more passage for active Carbon diffusion, and the thickness of the alloy gradient layer being added with rare earth element is increased rapidly.
The rare earth that the present invention adds, inhibits grain growth in the sintering process of step one, and in the cementation process of step 2, it is more tiny that interpolation rare earth alloy crystal grain does not still add alloy, so the last alloy surface crystal grain formed is comparatively tiny; Tiny crystal grain facilitates the carrying out of carburization reaction simultaneously, and more Co, toward Wimet internal migration, makes the low Co in top layer, small grains, and then improves the hardness on Wimet top layer.Due to the quick generation of gradient layer and the past interior migration of Co, make in alloy, to there is a large amount of scarce carbon phase (W
3co
3c or W
6co
6c), when there being C to infiltrate, scarce carbon is on good terms and is reacted rapidly with C, this just makes in whole reaction process, just can realize the control after gradient layer by controlling carburizing time, this is that the Wimet obtaining high-quality provides prerequisite, and this is also that prior art is very inaccessible.Simultaneously due to the increase of Thickness of Gradient Layer, make the scarce carbon in Wimet maintain a reasonable level mutually, this guarantees the toughness of Wimet.
In a word, by the Perfect Matchings of raw material and preparation technology, obtain the controlled and Wimet that hardness and intensity are all good of Thickness of Gradient Layer fast.
Accompanying drawing explanation
Fig. 1 is the 80min carburizing Wimet low power BSE photo of embodiment 1;
Fig. 2 is the outer crystal grain photo of 80min carburizing Wimet high power of embodiment 1;
Fig. 3 is the 80min carburizing Wimet high power middle layer crystal grain photo of embodiment 1;
Fig. 4 is the 80min carburizing Wimet high power internal layer crystal grain photo of embodiment 1.
Fig. 5 is the 80min carburizing Wimet electron probe microanalysis (EPMA) result of embodiment 1.
Fig. 6 is that the carburizing Wimet of embodiment 1 adds Y
2o
3do not add Y
2o
3sample cross-breaking strength comparison diagram.
As can be seen from Figure 1 Wimet presents obvious three-decker after over carburizing, and this is caused by different Co content distribution.
As can be seen from Figure 2 alloy outer contains a small amount of black phase Co, and white phase WC has certain grain growth.
As can be seen from Figure 3 alloy interlayer black Co phase is obviously more, and WC grain is more outer less.
As can be seen from Figure 4 alloy internal layer content grey lacks carbon phase, illustrates that inside carburization reaction does not occur, and internal grain is also more outer more tiny.
As can be seen from Figure 5 alloy Co content is first increased by outer and interior, rear reduction; Add y alloy to compare and do not add alloy, higher and accelerate the carrying out of carburization reaction at middle layer Co content.
As can be seen from Figure 6 the alloy cross-breaking strength adding Y is significantly improved, and especially when 80min carburizing, alloy fracture strength ratio does not add alloy height about 400MPa.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1:
Step one
The poor carbon cemented carbide powder of configuration containing rare earth element: described containing in the poor carbon cemented carbide powder of rare earth element, comprises by percentage to the quality:
WC powder 87.5%; Co powder 6%; W powder 6%; Rare earth oxide Y
2o
3, wherein Y accounts for 0.5% of the poor carbon cemented carbide powder total mass containing rare earth element; Described is 5.22wt.% containing the middle total content of carbon in the poor carbon cemented carbide powder of rare earth element; Described rare earth element y is by Y
2o
3obtain after reduction; The granularity of described WC powder is 2 μm; The granularity of described Co powder is 2.0 μm; The granularity of described W powder is 1.5 μm; Described Y
2o
3the granularity of powder is 1.5 μm; Its preparation process is: will join the WC powder, Co powder, W powder, the Y that get
2o
3dry grinding 2 hours, mixing, in order to make Y
2o
3be reduced to Y, heat 30 minutes in 950 DEG C of hydrogen atmospheres, reaction formula is Y
2o
3+ 3H
2=2Y+3H
2o; Cooling, obtains the poor carbon cemented carbide powder containing rare earth element;
The poor carbon cemented carbide powder obtained containing rare earth element is last, it is mixed with caking agent paraffin, then press forming pressure sintering, obtains poor carbon presintering matrix; Its detailed process is: will in mass ratio, caking agent: the poor carbon cemented carbide powder=1:50 containing rare earth element, by caking agent paraffin and the poor carbon cemented carbide powder containing rare earth element, load in ball mill, after allocating abrading-ball into by ball material mass ratio 4:1, with the rotating speed of 400rpm, carry out enforcement ball milling 24h in the oil, after wet-milling is complete, spray-drying process, obtains the standby material that granularity is 1.5 μm, standby material is under 200MPa after press forming, first dewax, then through pressure sintering, obtain poor carbon presintering matrix; During pressure sintering, controlled atmosphere is argon gas atmosphere, pressure is 6MPa, temperature is 1430 DEG C, the time is 40min; Obtain poor carbon presintering matrix;
Step 2
A series of for step one gained poor carbon presintering matrix is placed in hydrogen atmosphere, with solid sheet graphite for carbon source, carries out carburizing treatment 40 ~ 100 minutes at 1420 DEG C, obtain gradient hard alloy; Detect the performance of different carburizing time products therefrom;
Its concrete test item and detected result are in table 1
Table 1
Comparative example 1
Other conditions are completely consistent with embodiment 1, and just do not add rare earth element y, its concrete test item and detected result are in table 2
Table 2
In embodiment 1 with comparative example 1
First alloy surface polishes by detection graded alloy thickness approach, polishing, BSE pattern is taked under scanning electronic microscope (SEM), observe alloy surface gradient layer under low power, SEM photo calculates its Thickness of Gradient Layer under Image ProPlus software.
The Co content of alloy outer is by electron probe microanalysis (EPMA) (EPMA)
Can be found out by table 1 and table 2:
Graded alloy prepared by the embodiment of the present invention 1, after the carburizing of 40 ~ 100 minutes, hardness all reaches more than 91HRA, improves slightly a little than ordinary rigid alloy.Material bending strength adopts Instron mechanical test instrument bending strength to carry out test and characterizes, and finds to add Y
2o
3alloy bending strength all at more than 1600MPa, improving more than 200MPa than not adding alloy, about improving 10 ~ 20%, improve than conventional homogeneous Wimet and reach 30%.It can also be seen that, under identical car-burization condition, the formation speed of gradient layer of the present invention is far superior to the Wimet not adding rare earth element simultaneously.
Embodiment 2:
Other condition and embodiment 1 completely the same, just changed rare earth element into La, its content is 0.7wt%, by Y
2o
3change La into
2o
3, reduction La
2o
3temperature be 1050 DEG C, the time is heat 40 minutes, carburizing temperature is 1450 DEG C; Its concrete test item and detected result are in table 3
Table 3
Comparative example 2
Other condition is completely consistent with embodiment 2, and just do not add rare-earth elements La and eliminate the reducing process to rare-earth oxidation, its concrete test item and detected result are in table 4
Table 4
Can find out from table 3, table 4 after the carburizing of 40 ~ 100 minutes, hardness all reaches more than 91HRA, improves slightly a little than ordinary rigid alloy.Material bending strength adopts Instron mechanical test instrument bending strength to carry out test and characterizes, find that the alloy bending strength of adding La is all at more than 1600MPa, improving more than 200MPa than not adding alloy, about improving 10 ~ 20%, improve than conventional homogeneous Wimet and reach 30%.It can also be seen that, under identical car-burization condition, the formation speed of gradient layer of the present invention is far superior to the Wimet not adding rare earth element simultaneously.
Embodiment 3:
Other condition and embodiment 1 completely the same, just changed rare earth element into Ce, its content is 0.6wt%, by Y
2o
3change CeO into
2, reduction CeO
2temperature be 1100 DEG C, the time, carburizing temperature was 1460 DEG C for heat 30 minutes, compacting pressure is 300MPa; Its concrete test item and detected result are in table 5.
Table 5
Comparative example 3
Other condition is completely consistent with embodiment 3, and just do not add rare earth element ce and eliminate the reducing process to rare-earth oxidation, its concrete test item and detected result are in table 6
Table 6
Can find out from table 5, table 5 after the carburizing of 40 ~ 100 minutes, hardness all reaches more than 91HRA, improves slightly a little than ordinary rigid alloy.Material bending strength adopts Instron mechanical test instrument bending strength to carry out test and characterizes, except carburizing time 100min sample, add the alloy bending strength of Ce all at more than 2100MPa, more than 200MPa is improved than not adding alloy, about improve 10 ~ 20%, improve than conventional homogeneous Wimet and reach 20%.It can also be seen that, under identical car-burization condition, the formation speed of gradient layer of the present invention is far superior to the Wimet not adding rare earth element simultaneously.
Claims (9)
1. add the method that rare earth element prepares gradient hard alloy fast, it is characterized in that, comprise the steps:
Step one
By containing after the poor carbon cemented carbide powder press forming of rare earth, pressure sintering, obtains poor carbon presintering matrix; Described poor carbon cemented carbide powder comprises by percentage to the quality:
WC 78～88％；
Co 5.5～12％；
Rare earth element 0.3-1.2%;
W simple substance 5-12%;
Step 2
Poor for step one gained carbon presintering matrix is placed in hydrogen atmosphere, carries out carburizing treatment 40 ~ 120 minutes at 1400 ~ 1460 DEG C, obtain gradient hard alloy; In described gradient hard alloy, Thickness of Gradient Layer is 200 ~ 3000 μm.
2. a kind of method of adding rare earth element and preparing gradient hard alloy fast according to claim 1, is characterized in that: described poor carbon cemented carbide powder comprises by percentage to the quality:
WC 82-88％；
Co 5.5-10％；
Rare earth element 0.5-1.0%;
W simple substance 5-10%.
3. a kind of method of adding rare earth element and preparing gradient hard alloy fast according to claim 1, is characterized in that: described poor carbon cemented carbide powder comprises by percentage to the quality:
WC 84-86％；
Co 6-8％；
Rare earth element 0.5-0.7%;
W simple substance 6-8%.
4. a kind of method of adding rare earth element and preparing gradient hard alloy fast according to claim 1-3 any one, is characterized in that: the described poor carbon cemented carbide powder containing rare earth is prepared by following proposal:
Component by design is joined after WC powder, Co powder, W powder, the rareearth oxidate powder got mix, be reduced to rare earth oxide in a hydrogen atmosphere and be converted into rare earth metal completely, then obtain through wet-milling, drying, granulation the poor carbon cemented carbide powder containing rare earth that granularity is 1.5-3.0 μm.
5. a kind of method of adding rare earth element and preparing gradient hard alloy fast according to claim 4, is characterized in that: the granularity of described WC powder is 2.0 ~ 5.0 μm; The granularity of described Co powder is 1.5-3.5 μm; The granularity of described W powder is 1.8-3.5 μm; The granularity of described rareearth oxidate powder is 1.5-3.0 μm.
6. a kind of method of adding rare earth element and preparing gradient hard alloy fast according to claim 4, is characterized in that: described rare-earth oxidation is selected from Y
2o
3, La
2o
3, CeO
2in at least one.
7. a kind of method of adding rare earth element and preparing gradient hard alloy fast according to claim 4, it is characterized in that: the component by design is joined after WC powder, Co powder, W powder, the rareearth oxidate powder got mix, reduce in hydrogen atmosphere, reduction temperature is 850 ~ 1100 DEG C, the time is 30 ~ 60 minutes.
8. a kind of method of adding rare earth element and preparing gradient hard alloy fast according to claim 1-3 any one, it is characterized in that: by the poor carbon cemented carbide powder containing rare earth after press forming under 100-300MPa, through pressure sintering, obtain poor carbon presintering matrix; During pressure sintering, control temperature is 1420 ~ 1450 DEG C, vacuum tightness is 6 × 10
-3-5 × 10
-4pa, pressure is 4-6MPa, and the time is 40-90min.
9. a kind of method of adding rare earth element and preparing gradient hard alloy fast according to claim 1-3 any one, is characterized in that: in step 2, carburizing carbon source used is selected from least one in compact crystal shape graphite, flaky graphite, aphanitic graphite.
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| CN105177336A (en) * | 2015-09-07 | 2015-12-23 | 中南大学 | Method for rapidly preparing extra-coarse crystalline grain gradient hard alloy |
| CN106929844A (en) * | 2017-03-29 | 2017-07-07 | 大连理工大学 | A kind of method that surface laser Alloying Treatment is carried out to shielding tunnel excavator hobboing cutter cutter ring |
| CN112126811A (en) * | 2020-09-25 | 2020-12-25 | 长沙而道新能源科技有限公司 | Porcelain formula and production process |
| CN112342447A (en) * | 2020-10-28 | 2021-02-09 | 哈工宁伯医疗科技泰州有限公司 | Preparation method of composite ceramic |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105177336A (en) * | 2015-09-07 | 2015-12-23 | 中南大学 | Method for rapidly preparing extra-coarse crystalline grain gradient hard alloy |
| CN106929844A (en) * | 2017-03-29 | 2017-07-07 | 大连理工大学 | A kind of method that surface laser Alloying Treatment is carried out to shielding tunnel excavator hobboing cutter cutter ring |
| CN112126811A (en) * | 2020-09-25 | 2020-12-25 | 长沙而道新能源科技有限公司 | Porcelain formula and production process |
| CN112342447A (en) * | 2020-10-28 | 2021-02-09 | 哈工宁伯医疗科技泰州有限公司 | Preparation method of composite ceramic |
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|---|---|
| CN104388717B (en) | 2017-04-19 |
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