CN104181180A - Testing method of inherent quality defect of ultra-coarse particle WC powder - Google Patents
Testing method of inherent quality defect of ultra-coarse particle WC powder Download PDFInfo
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Abstract
The invention discloses a testing method of an inherent quality defect of ultra-coarse particle WC powder. The testing method comprises the steps: testing a crystal loose growth defect and testing an incomplete carbonization defect. A sample cold mounting is observed by adopting ascanning electron microscopy, whether the crystal loose growth defect exists or not is analyzed and determined; whether the incomplete carbonization defect exists or nor is analyzed and determined by adopting an X-ray diffraction object. According to the testing method, a basic conception, a characterization method and a testing method of the inherent quality defect of the ultra-coarse particle WC powder are firstly provided so as to help an hard alloy enterprise detect the inherent quality of the ultra-coarse particle WC powder in real time, the quality level and the quality stability of ultra-coarse crystal and extraordinarily-coarse hard alloys are improved; a technical parameter is provided for optimizing a preparation process of the WC powder as a raw material of the ultra-coarse crystal and extraordinarily-coarse hard alloys. The testing method is suitable for industrialized application, and has the great importance on improving a production process of the WC powder and the inherent quality of the WC powder and improving the quality and the quality stability of the ultra-coarse crystal and extraordinarily-coarse hard alloys.
Description
Technical field
The present invention relates to a kind of method of inspection of super coarse particle WC powder inherent quality defect, belong to powdered metallurgical material technical field and modern analysis detection technique field.
Background technology
WC powder is the crucial starting material of WC base cemented carbide.The inherent quality of WC powder comprises unicity, the integrality of crystallization etc. of its thing phase.
Be later than ultra-fine cemented carbide about the research history of super coarse-grain and extraordinarily thick cemented carbide both at home and abroad, still the commitment in development.
Under the identical condition of binding metal content, with in traditional, compared with coarse-grain wimet, super thick and extraordinarily thick cemented carbide has high thermal conductivity, higher fracture toughness and red hardness, thermal fatigue resistance and thermal shock resistance preferably, be mainly used in work continuously (as the road surface plane milling) of the continuous exploitation (as coal mining, subway and tunnel construction) of soft rock under extreme operating condition condition and modern highway, bridge, stamping die that toughness and thermal fatigue resistance, thermal shock resistance are had relatively high expectations, cold heading die, roll etc., have boundless market outlook.
Prepare super thick and extraordinarily thick cemented carbide, conventionally need to adopt the super coarse particle WC powder of Fisher particle size >15 μ m as raw material.The preparation method of this class WC raw material mainly contains two classes:
(1) doping process: comprise tungsten oxide alkali-metal-doped → high temperature reduction (～1000 DEG C) → high temperature cabonizations (>2000 DEG C);
(2) wet hydrogen technique: comprise pure zirconia tungsten wet hydrogen high temperature reduction (～1000 DEG C) → high temperature cabonizations (>2000 DEG C).
Preparing super coarse particle WC powder must adopt super coarse particle W powder as raw material.The super coarse particle W powder of prior art preparation is all the principles based on W particle is sharply grown in external cause induction reduction process.In reduction process, W particle is sharply grown and is easily caused the formation of the loose growth defect of W crystal.This crystal defect has significant hereditary effect, can cause the formation of the loose growth defect of WC crystal.
On the other hand, because raw material W powder particles is thick, easily cause W, C to mix the appearance of inhomogeneous and the incomplete phenomenon of carbonization.The loose growth defect of WC crystal and the incomplete defect of carbonization all can cause the formation of wimet microstructure defect, the out of control and product quality level of alloy grain degree and the decline of constant product quality.
The current national standard about WC powder is (as GB/T 4295, GB/T 26055, GB/T26725, Deng) only relate to the external qualities such as the particle mean size of powder or specific surface area, chemical composition, presentation quality, all do not relate to the inherent quality that is independent of the WC powder outside powder size and chemical composition.How effective evaluation to hard alloy process stability and wimet heterogeneous microstructure and performance and stability thereof are had to the inherent quality of the WC powder of significant impact, is perplexed Cemented Carbide Enterprises circle always.Yi Jun, Zhang Li, king's Zhe, Deng having reported a kind of method (Chinese Tungsten Industry from WC – Co wimet heterogeneous microstructure parameter (mean grain size, adjacent degree, crystal grain distribute) and the sensitivity assessment WC powder inherent quality of mechanical property to wet-grinding technology and relative device, 2014,29 (2): 13 – 18).This method has good versatility, but need to test by alloy, is indirectly evaluation method of one, can not directly disclose the inherent quality defect of WC powder.The rationality of alloy experimental program and alloy experimental level all can affect reliability and the objectivity of experimental result.
Because WC powder belongs to fragile powder, in the time that powder exists obvious inherent quality defect, the fragility of powder can further increase.Conventional powder soaks copper quadrat method and easily causes the cracked of powder, has a strong impact on the objectivity to the judgement of powder intrinsic quality; Conventionally in X-ray diffraction instrument test process, X ray is to 2 microns of the penetration depth < of WC powder.The super coarse particle WC powder of Fisher particle size >15 μ m is directly carried out to X-ray diffraction material phase analysis cannot whether carbonization judges completely to powder.
Up to now, there is not yet report about key concept, characterizing method and the method for inspection thereof of WC powder inherent quality defect.
Summary of the invention
The object of the present invention is to provide a kind of method of inspection of super coarse particle WC powder inherent quality defect, to help Cemented Carbide Enterprises to detect in real time super coarse particle WC powder inherent quality, improve quality level and the quality stability of super coarse-grain and extraordinarily thick cemented carbide; For super coarse-grain and extraordinarily thick cemented carbide raw material WC powder optimum preparation condition, provide technical parameter.
The method of inspection of a kind of super coarse particle WC powder inherent quality defect of the present invention, described inherent quality defect refers to the loose growth defect of crystal and the incomplete defect of carbonization, the described method of inspection comprises the steps:
The first step: the inspection of the loose growth defect of crystal
WC powder is made to cold edge sample, adopt scanning electron microscope, observe cold edge sample polishing section; In visual field, search, while there is hole in discovery WC particle, adjust visual field, make WC individual particle image substantially be full of whole visual field, to the image taking photo in visual field;
Second step: the inspection of the incomplete defect of carbonization
By WC powder Po Sui Zhi – 120 orders, adopt X-ray diffractometer to analyze it, obtain X ray diffracting spectrum; Observing 2 θ is the collection of illustrative plates diffraction peak quantity between 25～55 °, determines the thing phase that each diffraction peak is corresponding.
The method of inspection of a kind of super coarse particle WC powder inherent quality defect of the present invention, in the first step, cold edge sample adopts the original supply state WC powder of Fisher particle size >15 μ m to make.
The method of inspection of a kind of super coarse particle WC powder inherent quality defect of the present invention, in the first step, the preparation method of cold edge sample comprises the steps:
(1) WC powder surface parcel
Sample WC powder to be checked is immersed in ethyl acetate and carries out ultrasound wave dispersion, and subsequent filtration, natural drying, obtains ethyl acetate parcel WC powder;
(2) cold edge sample moulding
The ethyl acetate parcel WC powder that step 1 is obtained is placed in cold edge resin, after stirring, injects mould, solidifies rear demoulding, obtains cold edge sample;
Cold edge resin is by liquid-state epoxy resin, dibutyl ester, and ethylenediamine composition, by adding 8～12 milliliters of dibutyl esters in every 100 grams of liquid-state epoxy resins, 7～10 milliliters of ethylenediamines are made into;
When cold edge sample moulding, first epoxy resin and dibutyl ester are stirred, then, ethyl acetate is wrapped up to WC powder and disperse wherein, then after adding ethylenediamine to stir in injected plastic mould, at room temperature leave standstill 30～50 minutes, curing and demolding;
(3) grinding and polishing
By wimet metallographic sample grinding and polishing method, cure and demold sample is carried out to grinding and polishing;
(4) corrosion
Adopt the potassium ferricyanide of fresh configuration and the equal-volume mixed solution of NaOH to corrode polishing sample, etching time is 3～6 minutes;
(5) corrosion sample is carried out to plated film conductive processing
Adopting plated film instrument is gold or the platinum film of 15～25 nanometers in the sample surfaces plating a layer thickness through corrosion treatment.
The method of inspection of a kind of super coarse particle WC powder inherent quality defect of the present invention, in the equal-volume mixed solution of the potassium ferricyanide and NaOH, the mass percent concentration of the potassium ferricyanide is 10～20%, the mass percent concentration 10～20% of NaOH.
The method of inspection of a kind of super coarse particle WC powder inherent quality defect of the present invention, in the first step, photo to WC particle in the visual field photographing is measured, when the average-size >=1, diagonal angle of photo Hole micron, assert that detected super coarse particle WC powder exists the loose growth of crystal inherent quality defect, described diagonal angle average-size refers to the mean value of the maximum diagonal-size of hole and minimum diagonal-size.
The method of inspection of a kind of super coarse particle WC powder inherent quality defect of the present invention, in second step, WC powder fragmentation, adopts ball-milling technology to carry out.
The method of inspection of a kind of super coarse particle WC powder inherent quality defect of the present invention, ball milling selects tumbling-type bowl mill to be undertaken by dry crumbling method, and ball milling parameter is: drum's speed of rotation is 26D
– 1/2～34D
– 1/2rev/min, D is ball milling bucket internal diameter, unit is rice; Wimet mill ball and WC powder mass ratio are 10:1～15:1; The broken time is 10～15 hours.
The method of inspection of a kind of super coarse particle WC powder inherent quality defect of the present invention, in second step, adopting MDI Jade software is that collection of illustrative plates between 25～55 ° carries out the amplification of ordinate direction, observation analysis to 2 θ in the collection of illustrative plates obtaining, and observes W
2the diffraction peak of C thing phase, assert that detected super coarse particle WC powder exists the incomplete inherent quality defect of carbonization.
The method of inspection of a kind of super coarse particle WC powder inherent quality defect of the present invention, the loose growth defect of described crystal refers to that single powder particle inside exists the hole of average-size>=1, diagonal angle micron, and described diagonal angle average-size refers to the mean value of the maximum diagonal-size of hole and minimum diagonal-size; The incomplete defect of described carbonization refers to and in powder, has W
2c thing phase.
The method of inspection of a kind of super coarse particle WC powder inherent quality defect of the present invention, is defined as category-A hole when the average-size >=5, hole diagonal angle micron; Hole diagonal angle average-size, between 2～5 microns, is defined as category-B hole; Hole diagonal angle average-size, between 1～2 micron, is defined as C class hole.
Beneficial effect
Super coarse particle W powder is all the principles based on W particle is sharply grown in external cause induction reduction process.In reduction process, W particle is sharply grown and is easily caused the formation of the loose growth defect of W crystal.This growth defect has significant hereditary effect, can cause the formation of the loose growth defect of WC crystal.The present invention is based on the research of a large amount of experiments, observation and wimet heterogeneous microstructure and performance impact rule, the loose growth defect of WC crystal is classified, be category-A hole, category-B hole and C class hole, and the detection method of the loose growth defect of WC crystal is provided.
Because WC powder belongs to fragile powder, in the time that powder exists the loose growth defect of obvious crystal, the fragility of powder can further increase.Conventional powder soaks copper quadrat method and easily causes the cracked of powder, has a strong impact on the objectivity to the judgement of powder intrinsic quality.Cold edge sample preparation can not cause the generation of the cracked phenomenon of powder conventionally, but because the cracked phenomenon of powder easily appears in intrinsic fragility in sample grinding and polishing process.The present invention adopts before cold edge powder is carried out to the processing of ethyl acetate parcel, can effectively avoid the generation of the cracked phenomenon of powder in sample making course.In optical microscope or scanning electron microscope, observe cold edge sample powder polishing section, observe WC individual particle inside and whether have hole, select suitable enlargement factor, make WC individual particle image substantially be full of whole visual field, take a picture; Adopt image analysis software to analyze figure, judge on this basis whether powder exists the loose growth defect of crystal and defect type thereof; Effectively improve the reliability of the loose grown crystal defects detection of WC.
Tungsten powder carbonization is a diffusion reaction process from outward appearance to inner essence, and first W is converted into W
2c, then by W
2c is converted into WC.Conventionally in X-ray diffraction instrument test process, X ray is to 2 microns of the penetration depth < of WC powder.The super coarse particle WC powder of Fisher particle size >15 μ m is directly carried out to X-ray diffraction material phase analysis cannot whether carbonization judges completely to powder.The present invention is based on the fragility characteristic of WC and the inventor affects the grasp of rule on WC ball mill crushing degree on grinding efficiency and ball-milling technology about ball-milling technology, proposed WC powder sample to be checked to adopt tumbling-type bowl mill and dry crumbling method to carry out ball milling fully to expose the method in powder centre.
To poor thing phase, X-ray diffraction peak-to-peak by force a little less than, be easy to out in the cold if the small and weak diffraction peak of this class is not carried out to amplifying observation.The present invention adopts MDI Jade software to analyze X ray diffracting spectrum, in analytic process, X ray diffracting spectrum is carried out to ordinate direction and amplifies processing, observes 2 θ and in the collection of illustrative plates between 25～55 °, whether occurs W
2the diffraction peak of C thing phase, to judge whether there is the incomplete defect of carbonization in WC powder.
In the loose growth defect of WC powder crystal and the incomplete defect of carbonization other grade WC powder outside super coarse particle WC powder, may exist, but the high-lighting of problem is relatively not remarkable yet.Know-why of the present invention is adapted to the WC powder of other grade equally.
Optical microscope, has the notable features such as resolution is high, size scale precision height due to scanning electron microscope relatively, and the present invention adopts scanning electron microscope that the loose growth defect of WC powder crystal is observed and analyzed.The know-why of patent of the present invention is equally applicable to the microscope of other types.
In sum, the present invention has proposed key concept, characterizing method and the method for inspection thereof of super coarse particle WC powder inherent quality defect first, be suitable for industrial applications, the improvement to WC powder production technology and WC powder inherent quality, the quality to super coarse-grain and extraordinarily thick cemented carbide and quality stability promote significant.
Brief description of the drawings
Fig. 1 is that to have the Fisher particle size of A, B two class holes be the stereoscan photograph of the 200 type WC powder polishing sections of 22.1 microns simultaneously;
There is WC and W in Fig. 2
2the Fisher particle size of two kinds of thing phases of C is that the X-ray diffraction of the 200 type WC powders of 22.1 microns amplifies collection of illustrative plates;
Fig. 3 is that to have the Fisher particle size of A, B two class holes be the stereoscan photograph of the 200 type WC powder polishing sections of 22.1 microns simultaneously;
Fig. 4 is that to have the Fisher particle size of B, C two class holes be the stereoscan photograph of the 300 type WC powder polishing sections of 30.5 microns simultaneously;
Fig. 5 is that the inner Fisher particle size that does not have the loose growth defect of obvious crystal is the stereoscan photograph of the 300 type WC powder polishing sections of 32.0 microns;
Fig. 6 is that the inner Fisher particle size that does not have the loose growth defect of obvious crystal is the stereoscan photograph of the 300 type WC powder polishing sections of 32.0 microns;
Fig. 7 is that only to have the Fisher particle size of single WC thing phase be that the X-ray diffraction of the 300 type WC powders of 32.0 microns amplifies collection of illustrative plates.
The corresponding alkali-metal-doped technique of Fig. 1, Fig. 3 and Fig. 4.Be raw material owing to having adopted super coarse particle W powder prepared by alkali-metal-doped technique, caused existing in WC powder the loose growth of obvious crystal inherent quality defect.
The corresponding wet hydrogen technique of Fig. 5 and Fig. 6.Because material purity is higher, reducing process control reasonable, grain growth mechanism is different from alkali-metal-doped technique, there is not obvious crystal defect in WC powder inside.
Due to electron microscopic observation sample preparation inappropriate technology, cause the appearance of the cracked phenomenon of powder as shown in Figure 3, be unfavorable for observation and judgement to powder crystal defect.
Due to W, C hybrid technique is improper and carbonization technique is improper, has caused the generation of the incomplete phenomenon of carbonization as shown in Figure 2.Take suitable W, C hybrid technique and carbonization technique can prepare the super coarse particle WC powder of single WC thing phase as shown in Figure 7.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1:
Sample to be checked is that Fisher particle size prepared by alkali-metal-doped technique, 2100 DEG C of high temperature cabonizations is the 200 type WC powders of 22.1 microns.
Prepare polishing section scanning electron microscopic observation sample according to following steps:
(1) the sample to be checked original supply state of 10 grams of random samplings is immersed in ethyl acetate and carries out ultrasound wave dispersion, subsequent filtration, natural drying;
(2) carry out cold edge sample preparation by process the ethyl acetate parcel WC powder obtaining through step 1, cold edge resin edge sample formula is as follows: 100 grams of liquid-state epoxy resins, 12 milliliters of dibutyl esters, 7 milliliters of ethylenediamines; Cold edge quadrat method is as follows: configure in proportion epoxy resin and dibutyl ester, and stir, ethyl acetate is wrapped up to WC powder and disperse wherein, then after adding ethylenediamine to stir in injected plastic mould, at room temperature leave standstill 30 minutes, curing and demolding;
(3) press wimet metallographic sample grinding and polishing method to cure and demold sample grinding and polishing;
(4) adopt 20% potassium ferricyanide of fresh configuration and the equal-volume mixed solution of 20% NaOH to corrode polishing sample, etching time is 4 minutes;
(5) adopt ion sputtering film coating instrument to carry out gold-plated conductive processing to corrosion sample, golden film thickness is 15～25 nanometers.
In scanning electron microscope, observe the powder polishing section through plated film conductive processing, observe WC individual particle inside and whether have hole, taken a picture in the visual field that has hole.Fig. 1 is the stereoscan photograph of powder polishing section.According to grain size, the enlargement factor that Fig. 1 selects is 2000 times.As shown in Figure 1, in figure, individual particle WC powder is polycrystal powder, and crystal boundary is clear and legible.Adopt ImageJ image analysis software to measure Fig. 1 Hole size, result shows, in figure, the maximum diagonal-size of maximum hole is up to 32 microns, and a crystal grain in figure is inner, and to have 1 diagonal angle average-size be the category-B hole of 2.1 microns.Known according to measurement result, in powder, there are A, B two class holes simultaneously.
Adopt tumbling-type bowl mill and dry crumbling method to carry out ball milling to the original supply state sample to be checked of random sampling.Select following ball milling parameter: ball milling bucket internal diameter is 92 millimeters, WC powder weight is 50 grams, and drum's speed of rotation is 86 revs/min, and wimet mill ball and WC powder mass ratio are 10:1, and the broken time is 10 hours.After broken, cross 120 eye mesh screens.Adopt RigaukD/Max2500X x ray diffractometer x to analyze the powdered sample through ball-milling treatment.Adopt MDI Jade6.5 software to analyze X ray diffracting spectrum, in analytic process, X ray diffracting spectrum is carried out to ordinate direction and amplify processing, observe 2 θ and in the collection of illustrative plates between 25～55 °, whether occur W
2the diffraction peak of C thing phase.Fig. 2 amplifies collection of illustrative plates through the X-ray diffraction of ball-milling treatment sample.As seen from Figure 2, in sample, there is WC and W simultaneously
2two kinds of thing phases of C, there is the incomplete inherent quality defect of carbonization in sample.
Comparative example 1:
Prepare polishing section scanning electron microscopic observation sample according to following steps:
(1) cold edge resin edge sample formula is as follows: 100 grams of liquid-state epoxy resins, 12 milliliters of dibutyl esters, 7 milliliters of ethylenediamines; Cold edge quadrat method is as follows: configure in proportion epoxy resin and dibutyl ester, and stir, 10 grams are disperseed wherein without peracetic acid ethyl ester parcel original supply state WC powder to be checked that process, random sampling, after adding again ethylenediamine to stir in injected plastic mould, at room temperature leave standstill 30 minutes, curing and demolding;
(2) press wimet metallographic sample grinding and polishing method to cure and demold sample grinding and polishing;
(3) adopt 10% potassium ferricyanide of fresh configuration and the equal-volume mixed solution of 10% NaOH to corrode polishing sample, etching time is 6 minutes;
(4) adopt ion sputtering film coating instrument to carry out gold-plated conductive processing to corrosion sample, golden film thickness is 15～25 nanometers.
In scanning electron microscope, observe the powder polishing section through plated film conductive processing, observe WC individual particle inside and whether have hole, taken a picture in the visual field that has hole.Fig. 3 is the stereoscan photograph of powder polishing section.According to grain size, the enlargement factor that Fig. 3 selects is 2000 times.As seen from Figure 3, because powder is processed without peracetic acid ethyl ester parcel, be subject to the effect of external force in grinding and polishing process, there is serious cracked phenomenon in WC powder, but still can judge that in figure, individual particle WC powder is polycrystal powder, there are a large amount of holes in crystal grain inside.Adopt ImageJ image analysis software to measure Fig. 3 Hole size, result shows, has A, B two class holes in powder simultaneously, and wherein the maximum diagonal angle average-size of category-A hole is 7.1 microns, and the maximum diagonal angle average-size of category-B hole is 4.1 microns.
Embodiment 2:
Sample to be checked is that Fisher particle size prepared by alkali-metal-doped technique, 2400 DEG C of high temperature cabonizations is the 300 type WC powders of 30.5 microns.
Prepare polishing section scanning electron microscopic observation sample according to following steps:
(1) the sample to be checked original supply state of 13 grams of random samplings is immersed in ethyl acetate and carries out ultrasound wave dispersion, subsequent filtration, natural drying;
(2) carry out cold edge sample preparation by process the ethyl acetate parcel WC powder obtaining through step 1, cold edge resin edge sample formula is as follows: 100 grams of liquid-state epoxy resins, 8 milliliters of dibutyl esters, 10 milliliters of ethylenediamines; Cold edge quadrat method is as follows: configure in proportion epoxy resin and dibutyl ester, and stir, ethyl acetate is wrapped up to WC powder and disperse wherein, then after adding ethylenediamine to stir in injected plastic mould, at room temperature leave standstill 50 minutes, curing and demolding;
(3) press wimet metallographic sample grinding and polishing method to cure and demold sample grinding and polishing;
(4) adopt 20% potassium ferricyanide of fresh configuration and the equal-volume mixed solution of 20% NaOH to corrode polishing sample, etching time is 3 minutes;
(5) adopt ion sputtering film coating instrument to carry out platinum plating conductive processing to corrosion sample, platinum film thickness is 15～25 nanometers.
In scanning electron microscope, observe the powder polishing section through plated film conductive processing, observe WC individual particle inside and whether have hole, taken a picture in the visual field that has hole.Fig. 4 is the stereoscan photograph of powder polishing section.According to grain size, the enlargement factor that Fig. 4 selects is 1000 times.As shown in Figure 4, in figure, individual particle WC powder is polycrystal powder, and crystal grain inside exists a large amount of holes.Adopt ImageJ image analysis software to measure Fig. 4 Hole size, result shows, has B, C two class holes simultaneously, but do not have category-A hole in powder, and the maximum diagonal angle average-size of hole is 3.8 microns.
Adopt tumbling-type bowl mill and dry crumbling method to carry out ball milling to the original supply state sample to be checked of random sampling.Select following ball milling parameter: ball milling bucket internal diameter is 92 millimeters, WC powder weight is 80 grams, and drum's speed of rotation is 99 revs/min, and wimet mill ball and WC powder mass ratio are 13:1, and the broken time is 12 hours.After broken, cross 120 eye mesh screens.Adopt RigaukD/Max2500X x ray diffractometer x to analyze the powdered sample through ball-milling treatment.Adopt MDI Jade6.5 software to analyze X ray diffracting spectrum, in analytic process, X ray diffracting spectrum is carried out to ordinate direction and amplify processing, observe 2 θ and in the collection of illustrative plates between 25～55 °, whether occur W
2the diffraction peak of C thing phase.Result shows, amplifies collection of illustrative plates in ordinate direction, does not observe W
2, only there is single WC thing phase in the existence of C thing phase, sample does not exist the incomplete inherent quality defect of carbonization in sample.
Embodiment 3:
Sample to be checked is that Fisher particle size prepared by wet hydrogen technique, 2400 DEG C of high temperature cabonizations is the 300 type WC powders of 32.0 microns.
Prepare polishing section scanning electron microscopic observation sample according to following steps:
(1) the sample to be checked original supply state of 15 grams of random samplings is immersed in ethyl acetate and carries out ultrasound wave dispersion, subsequent filtration, natural drying;
(2) carry out cold edge sample preparation by process the ethyl acetate parcel WC powder obtaining through step 1, cold edge resin edge sample formula is as follows: 100 grams of liquid-state epoxy resins, 10 milliliters of dibutyl esters, 8 milliliters of ethylenediamines; Cold edge quadrat method is as follows: configure in proportion epoxy resin and dibutyl ester, and stir, ethyl acetate is wrapped up to WC powder and disperse wherein, then after adding ethylenediamine to stir in injected plastic mould, at room temperature leave standstill 40 minutes, curing and demolding;
(3) press wimet metallographic sample grinding and polishing method to cure and demold sample grinding and polishing;
(4) adopt 20% potassium ferricyanide of fresh configuration and the equal-volume mixed solution of 20% NaOH to corrode polishing sample, etching time is 4 minutes;
(5) adopt ion sputtering film coating instrument to carry out platinum plating conductive processing to corrosion sample, platinum film thickness is 15～25 nanometers.
In scanning electron microscope, observe the powder polishing section through plated film conductive processing, do not observe the inner phenomenon that has >=1 micron of hole of WC individual particle.Fig. 5 and Fig. 6 are the stereoscan photographs of powder polishing section.According to grain size, the enlargement factor that Fig. 5 selects is 5000 times, and the enlargement factor that Fig. 6 selects is 4000 times.As shown in Figure 5, in figure, individual particle WC powder is monocrystal, and the diagonal angle average-size of crystal grain is 43 microns.As shown in Figure 6, in figure, individual particle WC powder is polycrystal powder, and wherein the diagonal angle average-size of maximum crystal grain is 33 microns, and the diagonal angle average-size of minimum crystal grain is 6 microns.From Fig. 5 and Fig. 6, there is not the loose growth of crystal inherent quality defect in powder.
Adopt tumbling-type bowl mill and dry crumbling method to carry out ball milling to the original supply state sample to be checked of random sampling.Select following ball milling parameter: ball milling bucket internal diameter is 92 millimeters, WC powder weight is 70 grams, and drum's speed of rotation is 112 revs/min, and wimet mill ball and WC powder mass ratio are 15:1, and the broken time is 15 hours.After broken, cross 120 eye mesh screens.Adopt RigaukD/Max2500X x ray diffractometer x to analyze the powdered sample through ball-milling treatment.Adopt MDIJade6.5 software to analyze X ray diffracting spectrum, in analytic process, X ray diffracting spectrum is carried out to ordinate direction and amplify processing, observe 2 θ and in the collection of illustrative plates between 25～55 °, whether occur W
2the diffraction peak of C thing phase.Result shows, amplifies collection of illustrative plates in ordinate direction, does not observe W
2the existence of C thing phase.Fig. 7 amplifies collection of illustrative plates through the X-ray diffraction of ball-milling treatment sample.As seen from Figure 7, only having single WC thing phase in sample, there is not the incomplete inherent quality defect of carbonization in sample.
Claims (10)
1. a method of inspection for super coarse particle WC powder inherent quality defect, described inherent quality defect refers to the loose growth defect of crystal and the incomplete defect of carbonization, the described method of inspection comprises the steps:
The first step: the inspection of the loose growth defect of crystal
WC powder is made to cold edge sample, adopt scanning electron microscope, observe cold edge sample polishing section; In visual field, search, while there is hole in discovery WC particle, adjust visual field, make WC individual particle image substantially be full of whole visual field, to the image taking photo in visual field;
Second step: the inspection of the incomplete defect of carbonization
By WC powder Po Sui Zhi – 120 orders, adopt X-ray diffractometer to analyze it, obtain X ray diffracting spectrum; Observing 2 θ is the collection of illustrative plates diffraction peak quantity between 25～55 °, determines the thing phase that each diffraction peak is corresponding.
2. the method for inspection of a kind of super coarse particle WC powder inherent quality defect according to claim 1, is characterized in that: in the first step, cold edge sample adopts the WC powder of Fisher particle size >15 μ m to make.
3. the method for inspection of a kind of super coarse particle WC powder inherent quality defect according to claim 2, is characterized in that: in the first step, the preparation method of cold edge sample comprises the steps:
(1) WC powder surface parcel
Sample WC powder to be checked is immersed in ethyl acetate and carries out ultrasound wave dispersion, and subsequent filtration, natural drying, obtains ethyl acetate parcel WC powder;
(2) cold edge sample moulding
The ethyl acetate parcel WC powder that step 1 is obtained is placed in cold edge resin, after stirring, injects mould, solidifies rear demoulding, obtains cold edge sample;
Cold edge resin is by liquid-state epoxy resin, dibutyl ester, and ethylenediamine composition, by adding 8～12 milliliters of dibutyl esters in every 100 grams of liquid-state epoxy resins, 7～10 milliliters of ethylenediamines are made into;
When cold edge sample moulding, first epoxy resin and dibutyl ester are stirred, then, ethyl acetate is wrapped up to WC powder and disperse wherein, then after adding ethylenediamine to stir in injected plastic mould, at room temperature leave standstill 30～50 minutes, curing and demolding;
(3) grinding and polishing
By wimet metallographic sample grinding and polishing method, cure and demold sample is carried out to grinding and polishing;
(4) corrosion
Adopt the potassium ferricyanide of fresh configuration and the equal-volume mixed solution of NaOH to corrode polishing sample, etching time is 3～6 minutes;
(5) corrosion sample is carried out to plated film conductive processing
Adopting plated film instrument is gold or the platinum film of 15～25 nanometers in the sample surfaces plating a layer thickness through corrosion treatment.
4. the method for inspection of a kind of super coarse particle WC powder inherent quality defect according to claim 3, it is characterized in that: in the equal-volume mixed solution of the potassium ferricyanide and NaOH, the mass percent concentration of the potassium ferricyanide is 10～20%, the mass percent concentration 10～20% of NaOH.
5. according to the method for inspection of a kind of super coarse particle WC powder inherent quality defect described in claim 1～4 any one, it is characterized in that: in the first step, photo to WC particle in the visual field photographing is measured, when the average-size >=1, diagonal angle of photo Hole micron, assert that detected super coarse particle WC powder exists the loose growth of crystal inherent quality defect, described diagonal angle average-size refers to the mean value of the maximum diagonal-size of hole and minimum diagonal-size.
6. the method for inspection of a kind of super coarse particle WC powder inherent quality defect according to claim 1, is characterized in that: in second step, WC powder fragmentation, adopts ball-milling technology to carry out.
7. the method for inspection of a kind of super coarse particle WC powder inherent quality defect according to claim 6, is characterized in that: ball milling selects tumbling-type bowl mill to be undertaken by dry crumbling method, and ball milling parameter is: drum's speed of rotation is 26D
– 1/2～34D
– 1/2rev/min, D is ball milling bucket internal diameter, unit is rice; Wimet mill ball and WC powder mass ratio are 10:1～15:1; The broken time is 10～15 hours.
8. the method for inspection of a kind of super coarse particle WC powder inherent quality defect according to claim 1, it is characterized in that: in second step, adopting MDI Jade software is that collection of illustrative plates between 25～55 ° carries out the amplification of ordinate direction, observation analysis to 2 θ in the collection of illustrative plates obtaining, and observes W
2the diffraction peak of C thing phase, assert that detected super coarse particle WC powder exists the incomplete inherent quality defect of carbonization.
9. the method for inspection of a kind of super coarse particle WC powder inherent quality defect according to claim 1, it is characterized in that: the loose growth defect of described crystal refers to that single powder particle inside exists the hole of average-size>=1, diagonal angle micron, and described diagonal angle average-size refers to the mean value of the maximum diagonal-size of hole and minimum diagonal-size; The incomplete defect of described carbonization refers to and in powder, has W
2c thing phase.
10. the method for inspection of a kind of super coarse particle WC powder inherent quality defect according to claim 5, is characterized in that:, be defined as category-A hole when the average-size >=5, hole diagonal angle micron; Hole diagonal angle average-size, between 2～5 microns, is defined as category-B hole; Hole diagonal angle average-size, between 1～2 micron, is defined as C class hole.
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| CN105510105A (en) * | 2015-12-26 | 2016-04-20 | 山东泰山钢铁集团有限公司 | Method for rapidly determining phase content of double-phase stainless steel by using metallographic dyeing and software |
| CN107543745A (en) * | 2016-06-23 | 2018-01-05 | 中国科学院过程工程研究所 | A kind of cold edge method for making sample of superfine material |
| CN109576710A (en) * | 2018-12-07 | 2019-04-05 | 郑州航空工业管理学院 | A kind of chemical corrosion method removing carbide surface hard phase |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105067414A (en) * | 2015-08-17 | 2015-11-18 | 江西稀有稀土金属钨业集团有限公司 | System and method for observing hard alloy structure with scanning electron microscope |
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| CN109576710A (en) * | 2018-12-07 | 2019-04-05 | 郑州航空工业管理学院 | A kind of chemical corrosion method removing carbide surface hard phase |
| CN109576710B (en) * | 2018-12-07 | 2020-10-27 | 郑州航空工业管理学院 | Chemical corrosion method for removing hard phase on surface of hard alloy |
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