CN101638757A - Method for steel fiber surface anticorrosion and modified treatment - Google Patents
Method for steel fiber surface anticorrosion and modified treatment Download PDFInfo
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- CN101638757A CN101638757A CN200910063672A CN200910063672A CN101638757A CN 101638757 A CN101638757 A CN 101638757A CN 200910063672 A CN200910063672 A CN 200910063672A CN 200910063672 A CN200910063672 A CN 200910063672A CN 101638757 A CN101638757 A CN 101638757A
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Abstract
The invention discloses a method for steel fiber surface anticorrosion and modified treatment, which is as follows: steel fiber surface is degreased and added into silane coupling agent hydrolysate oralcoholysis liquid and stirred in the condition of room temperature or less than 70 DEG C so that silanol is coupled on the steel fiber surface and washed with clear water till the surface is neutraland aged in the temperature of 80-130 DEG C to cause that the silanol molecules on the surface of the steel fiber are crosslinked and forms firm FE-O-Si chemical bond with the Fe on the surface of the steel fiber, thus obtaining steel fiber with anticorrosion and modified treated surface. The method has easy available raw materials, simple technique operation, does not need complex devices, has high production efficiency and good modified effect.
Description
Technical field
The present invention relates to the method that a kind of steel fiber surface anticorrosion and modification are handled, the steel fiber surface coupling processing is played prevent the steel fiber corrosion thereby relate in particular to a kind of employing silane coupling agent, and improve the method for steel fiber and other material bonding strength.
Background technology
Steel fiber is widely used as the strongthener of matrix material.Because advantages such as high strength that it had, high-modulus, high temperature resistant and construction technology are simple and strengthen at pavement of road, cement concrete strengthens and aspect such as composite friction material enhancing obtains good application.Yet not surface treated steel fiber is easy corrosion, poor with matrix bond in construction and use, has influenced the weather resistance and the weathering resistance of its strongthener.The use range of steel fiber is restricted.
Silane coupling agent has obtained successful application in recent years in inorganic and metal-modified, it in metal-modified principle is: hydrolysis reaction takes place in the coupling agent at first moisture in the solvent contact, and then the generation dehydration reaction forms low poly structure, this oligopolymer forms hydrogen bond with the hydroxyl of metal material surface again, by heat drying condensation or dehydration reaction formation covalent linkage take place further, metal material surface is covered by silane coupling agent.But adopt silane coupling agent that the steel fiber modification is not seen the research report to improve its anticorrosion and processing method bonding strength.
Summary of the invention
The objective of the invention is to remedy the deficiencies in the prior art, provide a kind of steel fiber surface to carry out method anticorrosion and that modification is handled, adopt this method can strengthen steel fiber antiseptic property and with the bonding properties of matrix, overcome that it easily gets rusty in construction with in using, the shortcoming of matrix bond poor performance.
The technical scheme that realizes the object of the invention is: the method that a kind of steel fiber surface anticorrosion and modification are handled may further comprise the steps:
(1) with after the steel fiber surface oil removing, water washes to steel fiber surface and is neutral;
(2) under the room temperature, with ethanol, ethylene glycol and Virahol mixing obtain mixed solution, wherein, ethanol, ethylene glycol and the Virahol concentration of volume percent in mixed solution is respectively 40～80%, 10～30% and 10～30%, then with this mixed solution separately as solvent or with the deionized water mixing as solvent, making the concentration of volume percent of mixed solution in this solvent is 10%～100%, under agitation condition, in this solvent, slowly add silane coupling agent then, the pH value that drips acetate adjustment solution again is 3～4, it is transparent to continue to be stirred to solution, evenly, obtain concentration of volume percent and be 1～20% silane coupling agent hydrolyzed solution or alcoholysis liquid and (work as ethanol, the mixed solution of ethylene glycol and Virahol is during separately as solvent, obtain silane coupling agent alcoholysis liquid, work as ethanol, the mixed solution of ethylene glycol and Virahol and deionized water mixing obtain the silane coupling agent hydrolyzed solution during as solvent); Described silane coupling agent is the vinyltriethoxysilane coupling agent, the aminopropyl triethoxysilane coupling agent, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane coupling agent, in γ-methacryloxypropyl trimethoxy silane coupling agent or γ-mercaptopropyl trimethoxysilane coupling agent any or their mixed solution, vinyltriethoxysilane coupling agent in this mixed solution, the aminopropyl triethoxysilane coupling agent, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane coupling agent, the concentration of volume percent of γ-methacryloxypropyl trimethoxy silane coupling agent and γ-mercaptopropyl trimethoxysilane coupling agent is respectively: 20～50%, 20～50%, 0～20%, 0～20% and 0～20%;
(3) steel fiber after will cleaning joins in the reactive tank that fills silane coupling agent hydrolyzed solution or alcoholysis liquid, in room temperature or be heated to and be stirred well to silanol under the condition that is no more than 70 ℃ and be coupled at steel fiber surface, take out steel fiber then, be neutral with flushing with clean water steel fiber to its surface, filter moisture;
(4) it is molecule crosslinked and form " Fe-O-Si " chemical bond with the Fe of steel fiber surface the steel fiber after the coupling to be aged to the silanol of steel fiber surface under 80～130 ℃ of conditions, promptly obtains the steel fiber of handling through surface anticorrosion and modification.
Churning time is 10～30 minutes in the above-mentioned steps (3).
Digestion time is 30～120 minutes in the above-mentioned steps (4).
Compared with prior art, advantage of the present invention is:
1. the inventive method raw material is easily purchased, and technological operation is simple, does not need complex apparatus, the production efficiency height.
2. pass through the erosion resistance test shows of normal temperature, high temperature, high humidity and sour gas environment; adopt the inventive method modification handle the back steel fiber resistance to corrosion be improved significantly; illustrate that the fine and close protected silane layer of steel fiber surface can reasonable protection steel fiber contacts with surrounding medium and oxidized, played the purpose of the oxidation that prevents to get rusty.In addition, application in friction materials shows, strengthening friction materials with unmodified steel fiber compares, shock strength, bending strength and stable friction factor that the modification steel fiber strengthens friction materials obviously improve, wear rate also significantly reduces, the reinforcement of modification steel fiber and caking agent bonding force is described, and then has improved the various aspects of performance of its reinforced composite materials.In strengthening concrete application, strengthen sample with unmodified steel fiber and compare, modification steel fiber enhanced concrete sample intensity obviously improves, and has overcome the shortcoming that the ordinary steel fiber causes concrete strength to reduce because of corrosion.
Description of drawings
Fig. 1 is the process flow sheet that embodiment of the invention steel fiber surface anticorrosion and modification are handled;
Fig. 2 is the infrared spectrogram that later steel fiber is handled in embodiment 1 modification.
Embodiment
In order to understand content of the present invention better, the invention will be further described below in conjunction with the drawings and specific embodiments, but protection content of the present invention is not limited to following examples.
Embodiment 1
(1) with the steel fiber surface oil removing: take by weighing length 2～5mm, the weak point of diameter 0.05～0.2mm is cut steel fiber 50Kg, behind its surface degreasing, is neutral with flushing with clean water to steel fiber surface.The surface can subsidiary thin layer oily matter in the course of processing for steel fiber, and oil removing is cleaned in available alkalescence or other metal degreasing agent, and for example adopting steel fiber is that the method for soaking and stirring in 10～25w/v% soda ash solution of 40～100 ℃ is carried out oil removing to it in temperature.
(2) silane coupling agent hydrolysis: in reactive tank, add the 900L deionized water, add the mixed solution (ethanol, ethylene glycol and Virahol concentration of volume percent in this mixed solution be respectively 80%, 10% and 10%) of 100L again by ethanol, ethylene glycol and Virahol, after stirring, slowly add 25L vinyltriethoxysilane coupling agent while stirring, the pH value that drips acetate adjustment solution is 3～4, it is transparent, even to solution to continue stirring 40 minutes (general 10～60min is that hydrolyzable is complete), promptly obtains the hydrolyzed solution of silane coupling agent.
(3) steel fiber and silane coupling agent coupling: the steel fiber after will cleaning joins in the reactive tank that above-mentioned vinyltriethoxysilane coupling agent hydrating solution is housed, and at room temperature mechanical stirring 20 minutes to silanol is coupled at steel fiber surface.Steel fiber is taken out, be neutral, filter moisture with flushing with clean water to steel fiber surface.
(4) aging film forming: the steel fiber after the coupling is put into Electric heat oven, thermal ageing is 60 minutes under 100 ℃ temperature, make the silanol of steel fiber surface molecule crosslinked and form firm " Fe-O-Si " chemical bond with the Fe of steel fiber surface, promptly obtain the steel fiber through surface anticorrosion and modification processing, its process flow sheet as shown in Figure 1.
After modification disposes, adopt infrared spectra that steel fiber surface is tested, see Fig. 2.As can be seen from the figure, 2925cm wherein
-1The absorption peak at place is-CH
2-asymmetric stretching vibration, 1647cm
-1Absorption band be the stretching vibration of the C=C in the silane coupling agent, 3620cm
-1Absorption band be the hydroxyl of free state, 1100cm
-1The absorption peak at place is that the symmetry of the Si-O-Si that forms after the silane coupling agent coupling absorbs vibration peak, 920cm
-1The absorption peak at place is that the symmetry of Fe-O-Si absorbs vibration peak.Above result shows that polysiloxane film forms at steel fiber surface really.
The corrosion resistance of steel fiber, enhancing friction plate frictional behaviour, enhancing friction plate mechanical property and enhancing mechanical performance of concrete are tested after respectively modification being handled, and contrast with the respective performances of unmodified steel fiber, concrete data see Table 1,2,3 and 4.
Table 1. corrosion resistance test comparing result
In the above-mentioned table 1, do not have: without any corrosion; Slightly: visible a small amount of rust spot; Medium: visible more rust spot; Seriously: large stretch of corrosion.
Table 2. strengthens friction plate frictional behaviour comparing result
Table 3. strengthens friction plate mechanical property comparing result
| Strengthen the friction plate mechanical property | Unmodified steel fiber sample | Modification steel fiber sample |
| Shock strength (dj/cm 2) | ??4.3 | ??4.9 |
| Flexural strength (N/cm 2) | ??62 | ??71 |
| Maximum strain (mm/mm) | ??7.2 | ??7.5 |
Table 4. strengthens the mechanical performance of concrete comparing result
| Strengthen mechanical performance of concrete | Unmodified steel fiber sample | Modification steel fiber sample |
| Flexural strength (Mpa) | ??16.3 | ??18.7 |
Above data show that modification steel fiber anticorrosion effect compares obvious raising with unmodified steel fiber, and shock strength, bending strength and stable friction factor that the modification steel fiber strengthens friction materials obviously improve, and wear rate also significantly reduces.Adopt modification steel fiber enhanced concrete sample intensity to compare obvious raising with adopting unmodified steel fiber enhanced concrete sample.
Embodiment 2
(1) steel fiber surface oil removing: take by weighing length 2～5mm, the weak point of diameter 0.05～0.2mm is cut steel fiber 50Kg, with (deoiling method is with embodiment 1) behind its surface degreasing, is neutral with flushing with clean water to steel fiber surface.
(2) silane coupling agent hydrolysis: in reactive tank, add the 800L deionized water, add 200L again by ethanol, mixed solution (the ethanol of ethylene glycol and Virahol, ethylene glycol and the Virahol concentration of volume percent in this mixed solution is respectively 40%, 30% and 30%), after stirring, slowly add 50L aminopropyl triethoxysilane coupling agent while stirring and (perhaps adopt γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane coupling agent, in γ-methacryloxypropyl trimethoxy silane coupling agent or γ-mercaptopropyl trimethoxysilane coupling agent any), the pH value that drips acetate adjustment solution is 3～4, continue to stir 30 minutes transparent to solution, evenly, promptly obtain the hydrolyzed solution of silane coupling agent.
(3) steel fiber and silane coupling agent coupling: the steel fiber after will cleaning joins in the reactive tank that above-mentioned aminopropyl triethoxysilane coupling agent hydrating solution is housed, room temperature (or being no more than 70 ℃) down mechanical stirring 25 minutes to silanol be coupled at steel fiber surface.Steel fiber is taken out, be neutral, filter moisture with flushing with clean water to steel fiber surface.
(4) aging film forming: the steel fiber after the coupling is put into Electric heat oven, thermal ageing is 30 minutes under 105 ℃ temperature, make the silanol of steel fiber surface molecule crosslinked and form firm " Fe-O-Si " chemical bond, promptly obtain the steel fiber of handling through surface anticorrosion and modification with the Fe of steel fiber surface.
By the method identical steel fiber surface is tested, found to exist the characteristic absorbance of Si-O-Si key and Fe-O-Si key, confirm that polysiloxane film forms at steel fiber surface really with embodiment 1.By the method identical the steel strongthener is tested with embodiment 1, the result shows that modification steel fiber anticorrosion effect compares obvious raising than unmodified steel fiber, shock strength, bending strength and stable friction factor that the modification steel fiber strengthens friction materials obviously improve, and wear rate also significantly reduces.Adopt modification steel fiber enhanced concrete sample intensity to compare obvious raising with adopting unmodified steel fiber enhanced concrete sample.
Embodiment 3
(1) steel fiber surface oil removing: take by weighing length 2～5mm, the weak point of diameter 0.05～0.2mm is cut steel fiber 50Kg, with (deoiling method is with embodiment 1) behind its surface degreasing, is neutral with flushing with clean water to steel fiber surface.
(2) silane coupling agent hydrolysis: in reactive tank, add the 800L deionized water, add the mixed solution (ethanol, ethylene glycol and Virahol concentration of volume percent in this mixed solution be respectively 60%, 20% and 20%) of 200L again by ethanol, ethylene glycol and Virahol, after stirring, slowly add 50L vinyltriethoxysilane coupling agent while stirring, and then adding 50L aminopropyl triethoxysilane coupling agent, the pH value that drips acetate adjustment solution at last is 3～4, continue to stir 30 minutes transparent, even to solution, promptly obtain the hydrolyzed solution of silane coupling agent.
(3) steel fiber and silane coupling agent coupling: the steel fiber after will cleaning joins in the reactive tank that mixed type silane coupling agent hydrating solution is housed, room temperature (or being no more than 70 ℃) down mechanical stirring 15 minutes to silanol be coupled at steel fiber surface.Steel fiber is taken out, be neutral, filter moisture with flushing with clean water to steel fiber surface.
(4) aging film forming: the steel fiber after the coupling is put into Electric heat oven, thermal ageing is 45 minutes under 105 ℃ temperature, make the silanol of steel fiber surface molecule crosslinked and form firm " Fe-O-Si " chemical bond, promptly obtain the steel fiber of handling through surface anticorrosion and modification with the Fe of steel fiber surface.
By the method identical steel fiber surface is tested, found to exist the characteristic absorbance of Si-O-Si key and Fe-O-Si key, confirm that polysiloxane film forms at steel fiber surface really with embodiment 1.By the method identical the steel strongthener is tested with embodiment 1, the result shows that modification steel fiber anticorrosion effect compares obvious raising than unmodified steel fiber, shock strength, bending strength and stable friction factor that the modification steel fiber strengthens friction materials obviously improve, and wear rate also significantly reduces.Adopt modification steel fiber enhanced concrete sample intensity to compare obvious raising with adopting unmodified steel fiber enhanced concrete sample.
Embodiment 4
(1) steel fiber surface oil removing: take by weighing length 2～5mm, the weak point of diameter 0.05～0.2mm is cut steel fiber 50Kg, with (deoiling method is with embodiment 1) behind its surface degreasing, is neutral with flushing with clean water to steel fiber surface.
(2) silane coupling agent hydrolysis: in reactive tank, add the 100L deionized water, add 900L again by ethanol, mixed solution (the ethanol of ethylene glycol and Virahol, ethylene glycol and the Virahol concentration of volume percent in this mixed solution is respectively 70%, 15% and 15%), after stirring, slowly add 40L vinyltriethoxysilane coupling agent while stirring successively, 40L aminopropyl triethoxysilane coupling agent, 40L γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane coupling agent, 40L γ-methacryloxypropyl trimethoxy silane coupling agent and 40L γ-mercaptopropyl trimethoxysilane coupling agent, the pH value that drips acetate adjustment solution at last is 3～4, continue to stir 30 minutes transparent to solution, evenly, promptly obtain the hydrolyzed solution of silane coupling agent.
(3) steel fiber and silane coupling agent coupling: the steel fiber after will cleaning joins in the reactive tank that mixed type silane coupling agent hydrating solution is housed, and at room temperature mechanical stirring 30 minutes to silanol is coupled at steel fiber surface.Steel fiber is taken out, be neutral, filter moisture with flushing with clean water to steel fiber surface.
(4) aging film forming: the steel fiber after the coupling is put into Electric heat oven, thermal ageing is 100 minutes under 120 ℃ temperature, make the silanol of steel fiber surface molecule crosslinked and form firm " Fe-O-Si " chemical bond, promptly obtain the steel fiber of handling through surface anticorrosion and modification with the Fe of steel fiber surface.
By the method identical steel fiber surface is tested, found to exist the characteristic absorbance of Si-O-Si key and Fe-O-Si key, confirm that polysiloxane film forms at steel fiber surface really with embodiment 1.By the method identical the steel strongthener is tested with embodiment 1, the result shows that modification steel fiber anticorrosion effect compares obvious raising with unmodified steel fiber, shock strength, bending strength and stable friction factor that the modification steel fiber strengthens friction materials obviously improve, and wear rate also significantly reduces.Adopt modification steel fiber enhanced concrete sample intensity to compare obvious raising with adopting unmodified steel fiber enhanced concrete sample.
Embodiment 5
(1) steel fiber surface oil removing: take by weighing length 2～5mm, the weak point of diameter 0.05～0.2mm is cut steel fiber 50Kg, with (deoiling method is with embodiment 1) behind its surface degreasing, is neutral with flushing with clean water to steel fiber surface.
(2) silane coupling agent alcoholysis: in reactive tank, add the mixed solution (ethanol, ethylene glycol and Virahol concentration of volume percent in this mixed solution be respectively 80%, 10% and 10%) of 1000L by ethanol, ethylene glycol and Virahol, after stirring, slowly add 90L vinyltriethoxysilane coupling agent and 90L aminopropyl triethoxysilane coupling agent while stirring successively, the pH value that drips acetate adjustment solution at last is 3～4, continue to stir 30 minutes transparent, even to solution, promptly obtain the alcoholysis liquid of silane coupling agent.
(3) steel fiber and silane coupling agent coupling: the steel fiber after will cleaning joins in the reactive tank that mixed type silane coupling agent alcoholysis solution is housed, and is coupled at steel fiber surface being heated to 50～60 ℃ of following mechanical stirring 30 minutes to silanol.Steel fiber is taken out, be neutral, filter moisture with flushing with clean water to steel fiber surface.
(4) aging film forming: the steel fiber after the coupling is put into Electric heat oven, thermal ageing is 100 minutes under 120 ℃ temperature, make the silanol of steel fiber surface molecule crosslinked and form firm " Fe-O-Si " chemical bond, promptly obtain the steel fiber of handling through surface anticorrosion and modification with the Fe of steel fiber surface.
By the method identical steel fiber surface is tested, found to exist the characteristic absorbance of Si-O-Si key and Fe-O-Si key, confirm that polysiloxane film forms at steel fiber surface really with embodiment 1.By the method identical the steel strongthener is tested with embodiment 1, the result shows that modification steel fiber anticorrosion effect compares obvious raising with unmodified steel fiber, shock strength, bending strength and stable friction factor that the modification steel fiber strengthens friction materials obviously improve, and wear rate also significantly reduces.Adopt modification steel fiber enhanced concrete sample intensity to compare obvious raising with adopting unmodified steel fiber enhanced concrete sample.
Claims (3)
1. the method handled of steel fiber surface anticorrosion and modification is characterized in that may further comprise the steps:
(1) with after the steel fiber surface oil removing, water washes to steel fiber surface and is neutral;
(2) under the room temperature, with ethanol, ethylene glycol and Virahol mixing obtain mixed solution, wherein, ethanol, ethylene glycol and the Virahol concentration of volume percent in mixed solution is respectively 40～80%, 10～30% and 10～30%, then with this mixed solution separately as solvent or with the deionized water mixing as solvent, making the concentration of volume percent of mixed solution in this solvent is 10%～100%, under agitation condition, in this solvent, slowly add silane coupling agent then, the pH value that drips acetate adjustment solution again is 3～4, it is transparent to continue to be stirred to solution, evenly, obtaining concentration of volume percent is 1～20% silane coupling agent hydrolyzed solution or alcoholysis liquid; Described silane coupling agent is the vinyltriethoxysilane coupling agent, the aminopropyl triethoxysilane coupling agent, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane coupling agent, in γ-methacryloxypropyl trimethoxy silane coupling agent or γ-mercaptopropyl trimethoxysilane coupling agent any or their mixed solution, vinyltriethoxysilane coupling agent in this mixed solution, the aminopropyl triethoxysilane coupling agent, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane coupling agent, the concentration of volume percent of γ-methacryloxypropyl trimethoxy silane coupling agent and γ-mercaptopropyl trimethoxysilane coupling agent is respectively: 20～50%, 20～50%, 0～20%, 0～20% and 0～20%;
(3) steel fiber after will cleaning joins in the reactive tank that fills silane coupling agent hydrolyzed solution or alcoholysis liquid, in room temperature or be heated to and be stirred well to silanol under the condition that is no more than 70 ℃ and be coupled at steel fiber surface, take out steel fiber then, be neutral with flushing with clean water steel fiber to its surface, filter moisture;
(4) it is molecule crosslinked and form " Fe-O-Si " chemical bond with the Fe of steel fiber surface the steel fiber after the coupling to be aged to the silanol of steel fiber surface under 80～130 ℃ of conditions, promptly obtains the steel fiber of handling through surface anticorrosion and modification.
2. the method that steel fiber surface anticorrosion according to claim 1 and modification are handled is characterized in that: churning time is 10～30 minutes in the step (3).
3. the method that steel fiber surface anticorrosion according to claim 1 and modification are handled is characterized in that: digestion time is 30～120 minutes in the step (4).
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| CN102897765A (en) * | 2012-10-21 | 2013-01-30 | 荆州市江汉精细化工有限公司 | Method for preparing 3-aminopropyl triethoxy silane hydrolysate |
| CN104313563A (en) * | 2014-09-15 | 2015-01-28 | 湖南博云汽车制动材料有限公司 | Method for modification of steel fibers of semi-metallic formula brake disc |
| CN104480471A (en) * | 2014-11-27 | 2015-04-01 | 广州中国科学院工业技术研究院 | Silane coupling agent hydrolysate, as well as preparation method and application thereof |
| CN106892582A (en) * | 2017-03-06 | 2017-06-27 | 浙江大学 | A kind of composite coating based on silane coupler being modified for steel fiber surface |
| CN106927707A (en) * | 2017-03-06 | 2017-07-07 | 浙江大学 | A kind of processing method of silane coupler modified steel fiber surface |
| CN107473624A (en) * | 2017-06-26 | 2017-12-15 | 浙江大学 | A kind of cement-base composite material based on steel fibre after silane surface treatment |
| CN110002780A (en) * | 2019-04-12 | 2019-07-12 | 同济大学 | A kind of modified steel fibre and preparation method thereof |
| CN112960927A (en) * | 2021-01-25 | 2021-06-15 | 哈尔滨工业大学（深圳） | Nano material adsorption steel fiber and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102897765A (en) * | 2012-10-21 | 2013-01-30 | 荆州市江汉精细化工有限公司 | Method for preparing 3-aminopropyl triethoxy silane hydrolysate |
| CN104313563B (en) * | 2014-09-15 | 2017-05-31 | 湖南博云汽车制动材料有限公司 | A kind of modified method of steel fibre in semimetal formula brake block |
| CN104313563A (en) * | 2014-09-15 | 2015-01-28 | 湖南博云汽车制动材料有限公司 | Method for modification of steel fibers of semi-metallic formula brake disc |
| CN104480471B (en) * | 2014-11-27 | 2017-07-11 | 广州中国科学院工业技术研究院 | Silane coupler hydrolyzate and its preparation method and application |
| CN104480471A (en) * | 2014-11-27 | 2015-04-01 | 广州中国科学院工业技术研究院 | Silane coupling agent hydrolysate, as well as preparation method and application thereof |
| CN106892582A (en) * | 2017-03-06 | 2017-06-27 | 浙江大学 | A kind of composite coating based on silane coupler being modified for steel fiber surface |
| CN106927707A (en) * | 2017-03-06 | 2017-07-07 | 浙江大学 | A kind of processing method of silane coupler modified steel fiber surface |
| CN107473624A (en) * | 2017-06-26 | 2017-12-15 | 浙江大学 | A kind of cement-base composite material based on steel fibre after silane surface treatment |
| CN110002780A (en) * | 2019-04-12 | 2019-07-12 | 同济大学 | A kind of modified steel fibre and preparation method thereof |
| CN112960927A (en) * | 2021-01-25 | 2021-06-15 | 哈尔滨工业大学（深圳） | Nano material adsorption steel fiber and preparation method and application thereof |
| CN112960927B (en) * | 2021-01-25 | 2022-09-09 | 哈尔滨工业大学（深圳） | Nano-material adsorption steel fiber and preparation method and application thereof |
| CN113603422A (en) * | 2021-08-23 | 2021-11-05 | 崇德建材集团有限公司 | Anti-cracking recycled concrete |
| CN114457643A (en) * | 2022-01-22 | 2022-05-10 | 中国建设基础设施有限公司 | High-performance steel fiber graded broken stone mixture and preparation method thereof |
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