CN113281273B - Evaluation of TiB 2 Method for enhancing phase distribution uniformity degree in Cu mixed powder - Google Patents
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- 239000011812 mixed powder Substances 0.000 title claims abstract description 36
- 238000009826 distribution Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000002708 enhancing effect Effects 0.000 title claims description 12
- 238000011156 evaluation Methods 0.000 title claims description 7
- 239000000843 powder Substances 0.000 claims abstract description 76
- 239000010949 copper Substances 0.000 claims abstract description 44
- 238000012360 testing method Methods 0.000 claims abstract description 38
- 239000013307 optical fiber Substances 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000004907 flux Effects 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 210000004907 gland Anatomy 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- 230000003321 amplification Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- 230000003014 reinforcing effect Effects 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract 1
- 229910052802 copper Inorganic materials 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 7
- 238000004372 laser cladding Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
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- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
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Abstract
The invention discloses a method for evaluating TiB 2 Reinforcing in Cu mixed powderA method for phase distribution uniformity degree belongs to the technical field of laser additive manufacturing. TiB is prepared by the method of the invention 2 The method comprises the steps of adding particles into high-purity copper powder according to a proportion, placing a prepared powder bin at a test position corresponding to an integrating sphere, adjusting the position of an optical fiber, rotating the powder bin for three weeks at equal angular intervals of 45 degrees, enabling laser to irradiate at 8 equal radian (45 degrees) interval points on three circles with the radius of 1cm, 1.5cm and 2cm respectively, performing diffuse reflection through the integrating sphere, transmitting an optical signal received by a detector into a spectrometer, performing photoelectric conversion, signal amplification and analog-to-digital conversion, and finally calculating uniformity degree through computer processing and software; the method can evaluate TiB simply, rapidly and quantitatively 2 The degree of uniformity of phase distribution is enhanced in the Cu mixed powder.
Description
Technical Field
The invention relates to an evaluation TiB 2 A method for enhancing the uniformity degree of phase distribution in Cu mixed powder belongs to the technical field of laser additive manufacturing.
Background
Copper and its alloys have good plasticity, thermal conductivity and corrosion resistance, and thus have certain applications in the electronics, electrical industry and people's daily life. However, the copper alloy has the defects of low hardness, low tensile strength, poor wear resistance, high-temperature and easy oxidation, and the like, and limits the wider application of the copper in the industrial fields of high-voltage electrical appliances, microelectronics technologies and the like. In order to meet the new demands of the modern industry for copper and its alloys on the overall properties of copper-based materials, researchers often add ceramic particle reinforcement phases to the copper matrix, strengthening the copper matrix in a manner that the second phase particles retard dislocation motion. For example TiB 2 The particles have the advantages of high hardness, high melting point, high elastic modulus and the like, and simultaneously TiB 2 Particles are also a typical semiconductor material. Thus, adding an appropriate amount of TiB to the copper matrix 2 The particles not only can keep the good performances of electric conductivity, thermal conductivity, strong magnetic field resistance and the like of copper, but also can improve the hardness, strength and wear resistance of the copper-based composite material.
In recent years, with the continuous development of additive manufacturing technology, the laser cladding forming technology is one of the most promising surface modification technologies at present due to the advantages of simple equipment, high precision of formed parts and good surface quality. The laser cladding technology is a new technology with high economic benefit, can prepare high-performance alloy surface on a cheap metal substrate without affecting the property of a matrix, reduces the cost and saves precious and rare metal materials. Therefore, research and application of the laser cladding technology are very important in various industrial advanced countries in the world; the copper material has high reflectivity to laser, so that the absorptivity of the material to the laser in the laser cladding process is low; therefore, an appropriate amount of TiB is added to the copper powder prior to laser cladding 2 The particles can not only improve the absorptivity of the mixed powder to laser, but also enhance the comprehensive performance of the copper-based composite material. However, tiB 2 The uniformity of the distribution of the particles in the copper powder greatly influences the absorptivity of the mixed powder to laser light and the overall mechanical properties of the final formed copper-based composite, and therefore, there is an urgent need to find an evaluation of TiB 2 Method for enhancing the degree of uniformity of phase distribution in a Cu powder blend.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a spectrometer test method for approximate evaluation of TiB 2 Method for enhancing phase distribution uniformity degree in Cu mixed powder: detection of TiB with spectrometer 2 After diffuse reflection homogenization of light reflected by laser at different positions on the surface of Cu mixed powder by an integrating sphere, a diffuse reflection light signal received by a detector is transmitted to a spectrometer to be converted into an electric signal, finally, the electric signal is processed by a computer and calculated by software to display a light flux value on the spectrometer, and the fluctuation degree of the light flux value is calculated to approximately evaluate the addition of TiB in copper powder 2 Degree of uniformity of particle distribution.
The invention is realized by the following technical scheme: evaluation of TiB 2 The method for enhancing the uniformity degree of phase distribution in the Cu mixed powder comprises the following steps:
(1) TiB is prepared 2 The particles are added into the high-purity copper powder according to the proportion and mixedFully and uniformly mixing in a powder machine to form TiB 2 Placing the mixed powder of/Cu in a fully transparent quartz glass powder bin, closing a gland, placing the powder bin at a test position corresponding to an integrating sphere, adjusting an optical fiber to enter a number I clamping position, fixing the optical fiber, placing a laser spot at the moment on a circle (A circle) track with the radius of 1cm at the bottom of the powder bin, testing and recording a light flux value once by using a spectrometer after rotating the powder bin for 45 degrees, and so on, rotating the powder bin for one circle according to equal angles of 45 degrees, and recording the light flux value phi of each test Aa Where a=1..8, taking the maximum value Φ Max And a minimum value phi Min And calculating an arithmetic mean of 8 points denoted as Φ e Substituting the uniformity degree into the formula (1) to calculate the uniformity degree.
(2) The optical fiber is adjusted to enter the II-number clamping position and then is fixed, at the moment, the laser light spot rotates the powder bin for one circle at equal angular intervals of 45 degrees on a circle (B circle) track with the radius of 1.5cm at the bottom of the powder bin, and the value of each test light flux is recorded as phi Bb Where b=1..8, taking the maximum value Φ Max And a minimum value phi Min And calculates the arithmetic mean of 8 points as phi e Substituting the uniformity degree into the formula (1) to calculate the uniformity degree.
(3) After the optical fiber is adjusted to enter the III-type clamping position, fixing, rotating the powder bin for one circle according to the equal angular interval of 45 degrees on a circular (C-circle) track with the radius of 2cm at the bottom of the powder bin by using a laser spot, and recording the light flux value phi of each test Cc Where c=1..8, taking the maximum value Φ Max And a minimum value phi Min And calculating the arithmetic mean of 8 points as noted phi e Substituting the uniformity degree into the formula (1) to calculate the uniformity degree.
(4) Approximation TiB 2 The formula of the degree epsilon of uniformity of the distribution of the enhanced phase in the Cu mixed powder is as follows:
the grain size of the Cu powder is 40-50 mu m, and the purity is more than 99.5%; tiB (TiB) 2 Particle size is divided into two types: 2-10 mu m and 30-40 mu m, the purity is more than 99.6%, and the purity is more than one hundred percent in the mixed powderThe percentage is 15wt.%; the detection precision of the spectrometer is +/-0.01 lm, and the response time is 0.5s; the diameter of the used integrating sphere is 0.8m, the diffuse reflection coefficient of the internal white coating is 98.0%, and the integrating sphere has good spectrum diffuse reflection characteristic and the curvature radius is the same everywhere.
The test principle of the invention: due to TiB 2 The color of the enhancement phase is different from that of the Cu powder, the light absorption is different, if the mixing is uneven, the luminous flux difference measured at each test position is larger, and whether the powder is uniformly mixed is judged through the change of the luminous flux difference; the method comprises the following steps: the random polarized light emitted by the laser 5 is changed into linear polarized light after passing through the polarizer 4, and enters the optical fiber I clamping position 8, the optical fiber II clamping position 9 and the optical fiber III clamping position 10 respectively through the optical fiber 3 to be led into the 0.8m integrating sphere 11, the laser irradiates to the bottom of the powder bin 12, the reflected laser is reflected for many times by the diffuse reflection coating 1 in the integrating sphere 12, and finally is received by the detected light detector 2, and the detected diffuse reflection laser luminous flux value is displayed after photoelectric conversion, signal amplification and analog-digital conversion treatment of the spectrometer 6 and then computer processing and software calculation, and the test schematic diagram is shown as the attached figure 1 of the specification.
The invention has the beneficial effects that: can effectively and rapidly approximate evaluate TiB after mechanical stirring and mixing are uniform 2 Enhanced phase distribution uniformity in the Cu mixed powder, thereby establishing TiB 2 Particle distribution uniformity degree and laser cladding TiB 2 The relationship among microstructure, quality and mechanical property of Cu mixed powder forming part is studied for laser cladding TiB 2 The microstructure and performance of the Cu mixed powder formed part have very important reference value and theoretical basis.
Drawings
FIG. 1 is a spectrometer for TiB testing 2 Schematic diagram of distribution uniformity of Cu mixed powder.
1-diffuse reflective coating in the figure; 2-measuring the light detector; 3-optical fiber; a 4-polarizer; a 5-laser; 6-spectrometer; 7-a laser power supply; 8-I clamping position; no. 9-II clamping position; 10-III clamping positions; 11-integrating sphere; 12-powder bin.
Fig. 2 is a schematic view of the powder bin structure of the full transparent quartz glass.
In the figure: 13-a screw gland with an angle scale; 14-TiB 2 A Cu mixed powder; 15-a fully transparent quartz glass powder bin; 16-powder bin bottom.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the scope of the present invention is not limited to the above.
The invention provides a spectrometer test method for approximately evaluating TiB 2 Method for enhancing the degree of uniformity of phase distribution in a Cu powder blend. TiB is irradiated at the bottom of the powder bin 12 by laser 2 After the diffuse reflection coating 1 of the integrating sphere 11 is subjected to diffuse reflection for many times at different positions of the Cu mixed powder, light received by the photodiode type light measuring detector 2 is sequentially transmitted into the spectrometer 6 through the optical fiber 3, the polarizer 4 and the laser 5 to be subjected to photoelectric conversion, signal amplification and analog-to-digital conversion treatment, the detected light flux value is displayed on the spectrometer through computer treatment and software calculation, and the fluctuation degree of the light flux value is calculated to be converted into the degree of approximately evaluating the enhanced phase distribution uniformity in the mixed powder.
As shown in Table 1, the mixed powder was composed of pure Cu powder and TiB 2 Particle composition, cu powder at 85wt.%, tiB 2 The particles were 15wt.%, and TiB 2 Particle size is divided into two types: 2-10 μm and 30-40 μm; 3 kinds of mixed powder named as H1, H2 and H3 are prepared; taking a proper amount of each mixed powder, filling the powder bin 12, compacting, placing the powder bin 12 at a position corresponding to the integrating sphere 11, adjusting the optical fiber to enter the number I clamping position 8, enabling laser to irradiate the bottom of the powder bin 12, rotating the powder bin once every 45 degrees, and recording the light flux value tested once until the powder bin 12 rotates for one circle to finish the first cycle test; adjusting the optical fiber to enter a number II clamping position 9, and repeating the steps until the second cycle test is completed; adjusting the optical fiber to enter a III number clamping position 10, and repeating the steps until a third cycle test is completed; completing a mixed powder test after the three cycle tests are completed; by TiB 2 Detecting the change of the reflection laser luminous flux value of different positions on the surface of the mixed powder by the change of the reflection laser luminous flux value of different positions on the surface of the mixed powderThe degree of fluctuation of the values was used to approximate the degree of uniformity of the distribution of the enhanced phase in the mixed powder.
TABLE 1 TiB of different particle sizes in the same ratio 2 Granule and Cu powder ratio
Example 1
(1) Placing mixed powder H1 in a fully transparent quartz glass powder bin, covering tightly by a gland, placing the powder bin at a testing position corresponding to an integrating sphere (the bottom of the powder bin faces the inside of the integrating sphere), adjusting an optical fiber to enter a number I clamping position, and fixing, wherein a laser spot is positioned on a circular (A circle) track with the radius of 1cm at the bottom of the powder bin; after rotating the powder bin by 45 degrees, testing and recording one-time light flux value by using a spectrometer, and similarly rotating the powder bin by one circle according to the equal angles of 45 degrees, and recording each-time test light flux value as phi Aa Where a=1..8, taking the maximum value Φ Max And a minimum value phi Min And calculating an arithmetic mean of 8 points denoted as Φ e Substituting formula (1) calculates the degree of uniformity as shown in fig. 2.
(2) The optical fiber is adjusted to enter the II-number clamping position and then is fixed, at the moment, the laser light spot rotates the powder bin for one circle at equal angular intervals of 45 degrees on a circle (B circle) track with the radius of 1.5cm at the bottom of the powder bin, and the value of each test light flux is recorded as phi Bb Where b=1..8, taking the maximum value Φ Max And a minimum value phi Min And calculates the arithmetic mean of 8 points as phi e Substituting the uniformity degree into the formula (1) to calculate the uniformity degree.
(3) After the optical fiber is adjusted to enter the III-type clamping position, fixing, rotating the powder bin for one circle according to the equal angular interval of 45 degrees on a circular (C-circle) track with the radius of 2cm at the bottom of the powder bin by using a laser spot, and recording the light flux value phi of each test Cc Where c=1..8, taking the maximum value Φ Max And a minimum value phi Min And calculating the arithmetic mean of 8 points as noted phi e Substituting the uniformity degree into the formula (1) to calculate the uniformity degree.
(4) Approximation TiB 2 Cu mixed powderThe formula of the uniformity epsilon of the medium enhancement phase distribution is as follows:
the calculation results are shown in Table 2.
TABLE 2 light flux values and degree of uniformity of enhanced phase distribution corresponding to test points of mixed powder
Example 2
(1) Placing mixed powder H2 in a fully transparent quartz glass powder bin, covering a gland tightly, placing the powder bin at a testing position corresponding to an integrating sphere (the bottom of the powder bin faces the inside of the integrating sphere), adjusting an optical fiber to enter a number I clamping position, and fixing, wherein a laser spot is positioned on a circular (A circle) track with the radius of 1cm at the bottom of the powder bin; after rotating the powder bin by 45 degrees, testing and recording one-time light flux value by using a spectrometer, and similarly rotating the powder bin by one circle according to the equal angles of 45 degrees, and recording each-time test light flux value as phi Aa Where a=1..8, taking the maximum value Φ Max And a minimum value phi Min And calculating an arithmetic mean of 8 points denoted as Φ e Substituting the uniformity degree into the formula (1) to calculate the uniformity degree.
(2) The optical fiber is adjusted to enter the II-number clamping position and then is fixed, at the moment, the laser light spot rotates the powder bin for one circle at equal angular intervals of 45 degrees on a circle (B circle) track with the radius of 1.5cm at the bottom of the powder bin, and the value of each test light flux is recorded as phi Bb Where b=1..8, taking the maximum value Φ Max And a minimum value phi Min And calculates the arithmetic mean of 8 points as phi e Substituting the uniformity degree into the formula (1) to calculate the uniformity degree.
(3) After the optical fiber is adjusted to enter the III-type clamping position, fixing, rotating the powder bin for one circle according to the equal angular interval of 45 degrees on a circular (C-circle) track with the radius of 2cm at the bottom of the powder bin by using a laser spot, and recording the light flux value phi of each test Cc Where c=1..8, taking the maximum value Φ Max And at bestSmall value phi Min And calculating the arithmetic mean of 8 points as noted phi e Substituting the uniformity degree into the formula (1) to calculate the uniformity degree.
(4) Approximation TiB 2 The formula of the degree epsilon of uniformity of the distribution of the enhanced phase in the Cu mixed powder is as follows:
the calculation results are shown in Table 3.
TABLE 3 light flux values and degree of uniformity of enhanced phase distribution corresponding to test points of mixed powder
Example 3
(1) Placing mixed powder H3 in a fully transparent quartz glass powder bin, covering tightly by a gland, placing the powder bin at a testing position corresponding to an integrating sphere (the bottom of the powder bin faces the inside of the integrating sphere), adjusting an optical fiber to enter a number I clamping position, and fixing, wherein a laser spot is positioned on a circular (A circle) track with the radius of 1cm at the bottom of the powder bin; after rotating the powder bin by 45 degrees, testing and recording one-time light flux value by using a spectrometer, and similarly rotating the powder bin by one circle according to the equal angles of 45 degrees, and recording each-time test light flux value as phi Aa Where a=1..8, taking the maximum value Φ Max And a minimum value phi Min And calculating an arithmetic mean of 8 points denoted as Φ e Substituting the uniformity degree into the formula (1) to calculate the uniformity degree.
(2) The optical fiber is adjusted to enter the II-number clamping position and then is fixed, at the moment, the laser light spot rotates the powder bin for one circle at equal angular intervals of 45 degrees on a circle (B circle) track with the radius of 1.5cm at the bottom of the powder bin, and the value of each test light flux is recorded as phi Bb Where b=1..8, taking the maximum value Φ Max And a minimum value phi Min And calculates the arithmetic mean of 8 points as phi e Substituting the uniformity degree into the formula (1) to calculate the uniformity degree.
(3) Adjusting the optical fiber to enter III number clamping position and then fixing, and then laserThe light spot rotates the powder bin for a circle at equal angular intervals of 45 degrees on a circular (C-circle) track with the radius of 2cm at the bottom of the powder bin, and the light flux value phi of each test is recorded Cc Where c=1..8, taking the maximum value Φ Max And a minimum value phi Min And calculating the arithmetic mean of 8 points as noted phi e Substituting the uniformity degree into the formula (1) to calculate the uniformity degree.
(4) Approximation TiB 2 The formula of the degree epsilon of uniformity of the distribution of the enhanced phase in the Cu mixed powder is as follows:
the calculation results are shown in Table 4.
Table 4 light flux values and degree of uniformity of the distribution of the reinforcing phase corresponding to the test points of the mixed powder.
Claims (5)
1. Evaluation of TiB 2 The method for enhancing the uniformity degree of phase distribution in the Cu mixed powder is characterized by comprising the following steps of:
(1) TiB is prepared 2 The particles are added into high-purity copper powder according to a proportion, and fully and uniformly mixed in a powder mixer to form TiB 2 Placing the mixed powder of/Cu in a fully transparent quartz glass powder bin, closing a gland, placing the powder bin in a test position corresponding to an integrating sphere, adjusting an optical fiber to enter a number I clamping position, fixing, rotating the powder bin by 45 degrees on a circular track with the radius of 1cm at the bottom of the powder bin, testing and recording luminous flux once by using a spectrometer, and the like, rotating the powder bin for one circle according to the equal angles of 45 degrees, and recording the luminous flux value phi of each test Aa Where a=1..8, taking the maximum value Φ Max And a minimum value phi Min And calculating an arithmetic mean of 8 points denoted as Φ e Substituting the uniformity degree into the formula (1) to calculate the uniformity degree;
(2) Adjusting optical fiber to enter into the number II cardAfter the position is fixed, the laser light spot rotates the powder bin for a circle at equal angular intervals of 45 degrees on a circular track with the radius of 1.5cm at the bottom of the powder bin, and the light flux value phi of each test is recorded Bb Where b=1..8, taking the maximum value Φ Max And a minimum value phi Min And calculates the arithmetic mean of 8 points as phi e Substituting the uniformity degree into the formula (1) to calculate the uniformity degree;
(3) The optical fiber is adjusted to enter III-number clamping position and then fixed, a laser spot at the moment rotates the powder bin for one circle on a circular track with the radius of 2cm at the bottom of the powder bin at equal angular intervals of 45 degrees, and the value of each test light flux is recorded as phi Cc Where c=1..8, taking the maximum value Φ Max And a minimum value phi Min And calculates the arithmetic mean of 8 points as phi e Substituting the uniformity degree into the formula (1) to calculate the uniformity degree;
(4) Approximation TiB 2 The formula of the degree epsilon of uniformity of the distribution of the enhanced phase in the Cu mixed powder is as follows:
。
2. evaluating TiB according to claim 1 2 A method for enhancing the degree of uniformity of phase distribution in a Cu powder blend, characterized by: the grain diameter of the Cu powder is 40-50 mu m, and the purity is more than 99.5%.
3. Evaluating TiB according to claim 1 2 A method for enhancing the degree of uniformity of phase distribution in a Cu powder blend, characterized by: the TiB is 2 Particle size is divided into two types: 2-10 mu m and 30-40 mu m, the purity is more than 99.6%, tiB in the mixed powder 2 The percentage of particles was 15wt.%.
4. Evaluating TiB according to claim 1 2 A method for enhancing the degree of uniformity of phase distribution in a Cu powder blend, characterized by: the detection precision of the spectrometer is +/-0.011 m, and the response time is 0.5s.
5. Evaluating TiB according to claim 1 2 A method for enhancing the degree of uniformity of phase distribution in a Cu powder blend, characterized by: the integrating sphere used had a diameter of 0.8m and the internal white coating had a diffuse reflectance of 98.0%.
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| CN110744058A (en) * | 2019-11-01 | 2020-02-04 | 昆明理工大学 | Preparation method for in-situ synthesis of copper-based composite material |
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