CN111394991A - Method for grafting carbon nano tube on surface of carbon fiber based on plasma technology - Google Patents
Method for grafting carbon nano tube on surface of carbon fiber based on plasma technology Download PDFInfo
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- CN111394991A CN111394991A CN202010217976.XA CN202010217976A CN111394991A CN 111394991 A CN111394991 A CN 111394991A CN 202010217976 A CN202010217976 A CN 202010217976A CN 111394991 A CN111394991 A CN 111394991A
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 113
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 108
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 107
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 79
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 79
- 238000005516 engineering process Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 229920006334 epoxy coating Polymers 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 48
- 125000000524 functional group Chemical group 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- -1 functional group-activated carbon nanotubes Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 150000001721 carbon Chemical class 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 238000002715 modification method Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011157 advanced composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/06—Inorganic compounds or elements
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
- D06M10/025—Corona discharge or low temperature plasma
Abstract
The invention discloses a method for grafting carbon nanotubes on the surface of carbon fibers based on a plasma technology, which is characterized by comprising the following steps of: firstly, removing the epoxy coating on the surface of the carbon fiber, then activating the surface of the carbon fiber by adopting a plasma technology, oxidizing the carbon nanotube, and finally reacting the activated carbon fiber with the oxidized carbon nanotube to obtain the carbon fiber grafted with the carbon nanotube. The carbon fiber surface modification method adopted by the invention obviously improves the surface energy of the carbon fiber and provides a scheme for efficiently grafting the carbon nanotube on the carbon fiber. Meanwhile, the method also has the advantages of low cost, short preparation period, environmental protection and the like.
Description
[ technical field ]
The invention relates to the field of carbon fiber surface modification, in particular to a method for grafting carbon nanotubes on the surface of carbon fibers by adopting a plasma technology.
[ background art ]
The carbon fiber is used as a novel inorganic material with high specific strength, high specific modulus, high temperature resistance and corrosion resistance, and is widely applied to reinforcement of advanced composite materials as a typical high-performance fiber. However, the carbon fiber without surface treatment has low surface energy, few active functional groups and chemically inert surface, so that the carbon fiber is not well bonded with a resin matrix, and the mechanical property and the antistatic property of the resin are reduced. Therefore, the surface treatment is carried out on the carbon fiber, and active groups are introduced to the surface of the carbon fiber, so that the interface bonding quality of the carbon fiber and the composite material can be improved, and the antistatic performance of the composite material is improved.
The plasma and the material surface modification technology thereof are novel energy-saving, efficient and environment-friendly technologies, and are concerned by a plurality of frontier fields and interdisciplinary subjects at present. The plasma treatment of the fiber can introduce active groups into the surface of the carbon fiber, and meanwhile, the strength of the carbon fiber body cannot be damaged.
The carbon nano tube is a material with good mechanical property and self-lubricating property, and simultaneously has excellent electrical conductivity as metal, so that the problem of poor antistatic property of the polymer material can be improved by compounding the carbon nano tube into the polymer material.
[ summary of the invention ]
The invention aims to solve the problems of insufficient surface active groups, low bonding strength with resin and poor conductivity of the existing carbon fiber surface modification method, and provides a method for grafting carbon nanotubes on the surface of carbon fibers by adopting a plasma technology.
The method for grafting the carbon nano tube on the surface of the carbon fiber by the plasma technology is realized by the following steps:
(1) removal of epoxy coating on carbon fiber surface
Putting the carbon fiber bundle into a Soxhlet extractor, using acetone as a solvent, heating to 75-85 ℃, continuously evaporating the acetone and condensing in the Soxhlet extractor, and continuously cleaning impurities on the surface of the carbon fiber in distilled acetone for 30-40 h; then taking out the carbon fiber, and drying in an oven at the temperature of 80-90 ℃ for 4-6 h.
(2) Preparation of plasma activated carbon fiber
And (2) putting the carbon fiber into a cavity of a plasma processor for NH3 plasma modification, wherein the power of the plasma processor is 150W-260W, introducing high-purity NH3 with the gas flow rate of 15ml/min-40ml/min, the gas pressure is 1kPa-5kPa, and the processing time is 1h-2h to obtain the surface aminated carbon fiber.
(3) Oxidation treatment of carbon nanotubes
And refluxing and removing the photoresist of the carbon nano tube for 35 to 40 hours by using acetone under the water bath condition of 100 ℃, and oxidizing the carbon nano tube for 4 to 5 hours by using strong acid with the concentration of 14 to L to 16 to L to obtain the carbon nano tube with a large number of active functional groups generated on the surface.
(4) Grafted carbon nanotubes of activated carbon fibers
Immersing the carbon fiber with aminated surface into acetone solution of the carbon nano tube mixed with activated functional groups, performing ultrasonic treatment for 15min-30min, immersing for several hours at room temperature to graft a layer of carbon nano tube on the surface of the carbon fiber, washing with deionized water, putting the carbon fiber with the grafted carbon nano tube into an oven, and baking for 12h-15h at the temperature of 100-110 ℃ to obtain the carbon fiber with the surface grafted with the carbon nano tube.
Further, the carbon fiber in the step (1) is PAN-based carbon fiber, the diameter of the carbon fiber is 1-100 μm, and the specific surface area of the carbon fiber is 1-100 m 2/g-2/g.
Further, the mass of the carbon fiber of the step (1) and the volume of acetone are 1g:8m L.
Further, the strong acid in the step (3) is one or a mixture of concentrated sulfuric acid and concentrated nitric acid, wherein the concentration of the concentrated sulfuric acid is more than 90 wt%, and the concentration of the concentrated nitric acid is more than 70 wt%.
Further, the solid-to-liquid ratio of the carbon nanotubes to the strong acid in the step (3) is (5-10):100 g/ml.
Further, the diameter of the carbon nano tube in the step (3) is 10nm-100 nm.
Further, the specific surface area of the carbon nano tube is 100m2/g-300m 2/g.
Further, the mass ratio of the surface aminated carbon fiber to the functional group-activated carbon nanotube in the step (4) is 1: 0.1.
The invention has the beneficial effects that:
(1) the carbon fiber surface modification method adopted by the invention greatly improves the surface energy of the carbon fiber and provides a scheme for effectively improving the antistatic property and the mechanical property of the resin. Meanwhile, the method also has the advantages of low cost, short preparation period, environmental protection and the like.
(2) The ultrasonic infiltration treatment method adopted by the invention enables the carbon fiber bundles to be mutually separated and uniformly dispersed in the organic solvent, and can obviously improve the grafting probability of the activated carbon fibers and the carbon nano tubes. Meanwhile, the method also has the advantages of low cost, high efficiency, short preparation period and the like.
(3) The plasma technology adopted by the invention is used for treating the surface depth of the carbon fiber to be not more than 100 mu m, and the strength of the carbon fiber body can not be damaged.
[ description of the drawings ]
FIG. 1 shows the tensile strength of a single filament of carbon fiber grafted carbon nanotubes;
fig. 2 shows the interfacial shear strength of carbon fiber grafted carbon nanotubes.
[ detailed description of the invention ]
The first embodiment is as follows: the method for grafting the carbon nanotubes on the surface of the carbon fiber based on the plasma technology comprises the following steps:
(1) removal of epoxy coating on carbon fiber surface
Putting the carbon fiber bundle into a Soxhlet extractor, using acetone as a solvent, heating to 75-85 ℃, continuously evaporating the acetone and condensing in the Soxhlet extractor, and continuously cleaning impurities on the surface of the carbon fiber in distilled acetone for 30-40 h; then taking out the carbon fiber, and drying in an oven at the temperature of 80-90 ℃ for 4-6 h.
(2) Preparation of plasma activated carbon fiber
And (2) putting the carbon fiber into a cavity of a plasma processor for NH3 plasma modification, wherein the power of the plasma processor is 150W-260W, introducing high-purity NH3 with the gas flow rate of 15ml/min-40ml/min, the gas pressure is 1kPa-5kPa, and the processing time is 1h-2h to obtain the surface aminated carbon fiber.
(3) Oxidation treatment of carbon nanotubes
And refluxing and removing the photoresist of the carbon nano tube for 35 to 40 hours by using acetone under the water bath condition of 100 ℃, and oxidizing the carbon nano tube for 4 to 5 hours by using strong acid with the concentration of 14 to L to 16 to L to obtain the carbon nano tube with a large number of active functional groups generated on the surface.
(4) Grafted carbon nanotubes of activated carbon fibers
Immersing the carbon fiber with aminated surface into acetone solution of the carbon nano tube mixed with activated functional groups, performing ultrasonic treatment for 15min-30min, immersing for several hours at room temperature to graft a layer of carbon nano tube on the surface of the carbon fiber, washing with deionized water, putting the carbon fiber with the grafted carbon nano tube into an oven, and baking for 12h-15h at the temperature of 100-110 ℃ to obtain the carbon fiber with the surface grafted with the carbon nano tube.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the flow of the high-purity NH3 introduced in the step (2) is 15ml/min-30ml/min, and the gas pressure is 1kPa-4 kPa. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first and second embodiments in that: and (3) the power of the plasma processor in the step (2) is 150W-200W, and the processing time is 1.5h-2 h. The rest is the same as the first embodiment or the second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: and (3) refluxing and degumming the carbon nano tube in the step (2) for 35-37 h by using acetone under the water bath condition of 100 ℃. The others are the same as in one of the first to third embodiments.
Fifth embodiment five is different from the first to fourth embodiments in that the concentration of the strong acid in the step (3) is 14 mol/L-15 mol/L, and the time for the oxidation treatment of the carbon nanotubes is 4h-4.5 h.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: and (4) immersing the surface aminated carbon fiber in the acetone solution mixed with the carbon nano tube activated by the functional group for 15-20 min. The other is the same as one of the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: and (5) baking the carbon fiber grafted with the carbon nano tube in the oven at the temperature of 100-105 ℃ for 14-15 h. The other is the same as one of the first to sixth embodiments.
The following tests were used to verify the beneficial effects of the present invention:
example 1:
the method for grafting the carbon nanotubes on the surface of the carbon fiber based on the plasma technology is carried out according to the following steps:
(1) removal of epoxy coating on carbon fiber surface
Putting the carbon fiber bundle into a Soxhlet extractor, using acetone as a solvent, heating to 75 ℃, continuously evaporating the acetone and condensing in the Soxhlet extractor, and continuously cleaning impurities on the surface of the carbon fiber in distilled acetone for 40 h; the carbon fibers were then removed and dried in an oven at 80 ℃ for 6 h.
(2) Preparation of plasma activated carbon fiber
And (2) putting the carbon fiber into a cavity of a plasma processor for NH3 plasma modification, wherein the power of the plasma processor is 150W, introducing high-purity NH3 with the gas flow rate of 40ml/min, the gas pressure is 5kPa, and the processing time is 2h, so that the carbon fiber with the aminated surface is obtained.
(3) Oxidation treatment of carbon nanotubes
And (2) refluxing and removing the photoresist of the carbon nano tube by using acetone for 40h under the water bath condition of 100 ℃, and oxidizing the carbon nano tube by using strong acid with the concentration of 16 mol/L for 4h to obtain the carbon nano tube with a large number of active functional groups generated on the surface.
(4) Grafted carbon nanotubes of activated carbon fibers
Immersing the carbon fiber with aminated surface into acetone solution of the carbon nano tube mixed with activated functional groups, performing ultrasonic treatment for 15min, immersing for several hours at room temperature to graft a layer of carbon nano tube on the surface of the carbon fiber, washing with deionized water, putting the carbon fiber with the grafted carbon nano tube into an oven, and baking for 12 hours at the temperature of 110 ℃ to obtain the carbon fiber with the carbon nano tube grafted on the surface.
Table 1 relative contents of elements on the front and rear surfaces of the carbon fiber-grafted carbon nanotube. Table 2 contact angle and surface energy before and after carbon fiber treatment. It can be seen from table 1 that the carbon element content of the carbon fiber surface is significantly reduced and the nitrogen element content is significantly increased after the carbon fiber surface treatment. Therefore, the number of active polar functional groups on the carbon fiber surface after the treatment of the grafted carbon nano tube is greatly increased, and the interface performance of the carbon fiber material is obviously improved.
Table 2 contact angle and surface energy before and after the carbon fiber surface grafting treatment. From table 2, it can be seen that the contact angles of the carbon fibers after the surface treatment in water and ethylene glycol are both significantly reduced, and the surface energy is significantly improved, which indicates that the carbon nanotubes after the oxidation treatment can significantly improve the wettability of the carbon fiber surface, and is beneficial to improving the interface bonding capability of the carbon fibers and the resin material.
Fig. 1 and 2 are graphs comparing tensile strength and interfacial shear strength of carbon fibers before and after grafting carbon nanotubes prepared in example one. It is known that the tensile strength of the carbon fiber grafted carbon nanotube monofilament is increased from 3.81GPa of the precursor to 3.84GPa, and the tensile strength of the carbon fiber monofilament is not reduced. Meanwhile, the interfacial shear strength of the carbon fiber grafted carbon nanotube is improved to 136.5MPa from 81.6MPa of the precursor, and is improved by 67.3 percent. The carbon fiber is grafted by the carbon nano tube, so that the surface polarity of the carbon fiber is increased, the interface bonding of the carbon fiber and the resin matrix is improved, and the interface strength is obviously improved.
TABLE 1 relative contents of elements on front and back surfaces of carbon fiber grafted carbon nanotube
| Sample (I) | Cls(at.％) | Ols(at.％) | Nls(at.％) |
| Carbon fiber | 82.73 | 15.65 | 1.62 |
| Carbon fiber grafted with carbon nanotube | 68.66 | 17.81 | 13.53 |
TABLE 2 surface energy before and after carbon fiber surface grafting treatment
The above-mentioned embodiments of the present invention are intended to better explain the present invention, but the above-mentioned embodiments do not limit the scope of the present invention. Other variations or modifications may be made on the basis of the above description, which is not intended to be exhaustive, and all other variations or modifications encompassed by the present invention are intended to be included within the scope of the present invention as defined in the appended claims.
Claims (8)
1. A preparation method of carbon fiber surface grafted carbon nanotubes based on a plasma technology is characterized by comprising the following steps:
(1) removal of epoxy coating on carbon fiber surface
Putting the carbon fiber bundle into a Soxhlet extractor, using acetone as a solvent, heating to 75-85 ℃, continuously evaporating the acetone and condensing in the Soxhlet extractor, and continuously cleaning impurities on the surface of the carbon fiber in distilled acetone for 30-40 h; then taking out the carbon fiber, and drying in an oven at the temperature of 80-90 ℃ for 4-6 h;
(2) preparation of plasma activated carbon fiber
Putting the carbon fiber into a cavity of a plasma processor for NH3 plasma modification, wherein the power of the plasma processor is 150W-260W, introducing high-purity NH3 with the gas flow rate of 15ml/min-40ml/min, the gas pressure is 1kPa-5kPa, and the processing time is 1h-2h to obtain the surface aminated carbon fiber;
(3) oxidation treatment of carbon nanotubes
Refluxing and removing glue for 35-40 h by using acetone under the water bath condition of 100 ℃, and carrying out oxidation treatment on the carbon nanotube for 4-5 h by using strong acid with the concentration of 14 mol/L-16 mol/L to obtain the carbon nanotube with a large amount of active functional groups generated on the surface;
(4) grafted carbon nanotubes of activated carbon fibers
Immersing the carbon fiber with aminated surface into acetone solution of the carbon nano tube mixed with activated functional groups, performing ultrasonic treatment for 15min-30min, immersing for several hours at room temperature to graft a layer of carbon nano tube on the surface of the carbon fiber, washing with deionized water, putting the carbon fiber with the grafted carbon nano tube into an oven, and baking for 12h-15h at the temperature of 100-110 ℃ to obtain the carbon fiber with the surface grafted with the carbon nano tube.
2. The method for grafting carbon nanotubes on the surface of carbon fiber based on plasma technology as claimed in claim 1, wherein the carbon fiber in step (1) is PAN-based carbon fiber, the diameter of the carbon fiber is 1 μm-100 μm, and the specific surface area of the carbon fiber is 1m2/g-100m 2/g.
3. The method for grafting carbon nanotubes on the surface of carbon fiber based on the plasma technology as claimed in claim 1, wherein the mass of the carbon fiber and the volume of acetone in the step (1) are 1g:8m L.
4. The method for grafting carbon nanotubes on the surface of carbon fibers based on the plasma technology as claimed in claim 1, wherein the strong acid in step (3) is one or a mixture of concentrated sulfuric acid and concentrated nitric acid, wherein the concentration of the concentrated sulfuric acid is 90 wt% or more, and the concentration of the concentrated nitric acid is 70 wt% or more.
5. The method for grafting the carbon nanotubes on the surface of the carbon fiber based on the plasma technology as claimed in claim 1, wherein the solid-to-liquid ratio of the carbon nanotubes to the strong acid in the step (3) is (5-10):100 g/ml.
6. The method for grafting carbon nanotubes on the surface of carbon fibers based on the plasma technology as claimed in claim 1, wherein the diameter of the carbon nanotubes is 10nm-100 nm.
7. The method for grafting carbon nanotubes on the surface of carbon fiber based on plasma technology as claimed in claim 1, wherein the specific surface area of the carbon nanotubes in the step (3) is 100m2/g-300m 2/g.
8. The method for grafting carbon nanotubes on the surface of carbon fibers based on the plasma technology, as claimed in claim 1, wherein the mass ratio of the surface aminated carbon fibers to the functional group-activated carbon nanotubes in the step (4) is 1: 0.1.
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| CN113149526A (en) * | 2020-08-10 | 2021-07-23 | 河海大学 | Composite cement-based material and composite cement-based material sensor |
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Application publication date: 20200710 |