CN113072810B - Crosslinked starch reinforced composite shear thickening elastomer - Google Patents
Crosslinked starch reinforced composite shear thickening elastomer Download PDFInfo
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- CN113072810B CN113072810B CN202110339505.0A CN202110339505A CN113072810B CN 113072810 B CN113072810 B CN 113072810B CN 202110339505 A CN202110339505 A CN 202110339505A CN 113072810 B CN113072810 B CN 113072810B
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Abstract
The invention discloses a crosslinked starch reinforced composite shear thickening elastomer, and belongs to the technical field of composite material preparation. According to the invention, the crosslinked starch and the shear thickening glue are compounded to form a high-molecular network structure, so that the problem of cold flowability of the original shear thickening material is solved, and the shear thickening material has better processability, initial elastic modulus and elastic recovery capability, and is beneficial to maintaining the integral protective performance without attenuation in the long-time use process. The shear thickening elastomer prepared by the invention not only maintains good impact resistance, but also has excellent stability (namely no cold flow). The shear thickening elastomer is easy to encapsulate as a core material in the actual application process, and when the sealing property of a plane material is lost during breakage, the shear thickening elastomer cannot leak like shear thickening glue.
Description
Technical Field
The invention relates to a crosslinked starch reinforced composite shear thickening elastomer, belonging to the technical field of composite material preparation.
Background
With the improvement of safety consciousness of people, the market of protective buffer materials is gradually expanded, and various protective materials based on Shear Thickening Fluid (STF) and Shear Thickening Gel (STG) are increasingly concerned by researchers due to the characteristics of light weight and good protective performance; the shear thickening reinforcing material is in a liquid-like state at a low shear rate, the viscosity is rapidly increased under high dynamic load to be in a solid-like state, and the impact resistance and the damping performance of the shear thickening reinforcing material are greatly improved. At present, shear thickening fluid is widely applied and researched, but the shear thickening fluid has inherent defects, the encapsulation is difficult in use, dispersed phases are easy to settle, continuous phases are easy to volatilize, and therefore the overall performance is affected. The shear thickening glue is prepared by blending and heating silicone oil and boric acid, wherein in the heating process, hydroxyl terminated by the silicone oil is subjected to dehydration condensation with the boric acid, an element B brought by the boric acid has an empty p orbit, an atom O has redundant electrons, the two have weak attraction, and a B-O instantaneous cross-linking bond similar to a hydrogen bond is generated by sharing the electron pair. The generation and the breakage of the cross-linking bond have reversibility, and the strength is lower than that of a common chemical bond and higher than that of intermolecular force. Under normal conditions, macromolecule long chains in the shear thickening glue can be tangled; when the shear thickening glue is loaded by a small external force, macromolecules among the shear thickening glue can relatively slide, and the system can have enough time to open a B-O bond and entangle; when the external force load is large, the entanglement between the B-O bond and the macromolecule cannot be opened in time due to the short acting time, so that the overall viscosity is increased rapidly. However, the pure shear thickening glue has low initial viscosity, storage modulus and yield stress and has certain cold flow property in the long-term use process, so that the solution of the inherent defects of the shear thickening material becomes a new research direction.
Disclosure of Invention
[ problem ] to provide a method for producing a semiconductor device
The technical problem to be solved by the invention is to provide a shear thickening elastomer which has stable performance, no cold flow, good energy dissipation capability and good impact resistance.
[ technical solution ] A
Aiming at the problems in the prior art, the invention adopts the cross-linked starch and the shear thickening glue to compound to form a high-molecular network structure, solves the problem of cold flowability of the original shear thickening material, has better processability, initial elastic modulus and elastic recovery capability, and is beneficial to keeping the integral protective performance without attenuation in the long-time use process. The shear thickening elastomer prepared by the invention not only maintains good impact resistance, but also has excellent stability (namely no cold flow). The shear thickening elastomer is easy to encapsulate as a core material in the actual application process, and when the sealing property of a plane material is lost during breakage, the shear thickening elastomer cannot leak like shear thickening glue.
A first object of the present invention is to provide a crosslinked starch-reinforced composite shear thickening gum comprising a crosslinked starch and a shear thickening gum; the mass ratio of the cross-linked starch to the shear thickening glue is (1-6): (4-9). Wherein the cross-linked starch is used as filler.
Preferably, the mass ratio of the cross-linked starch to the shear thickening gum is (4-6): (4-6). The starch content is too high, and when external force is applied, the action between the starch and the shear thickening glue is too small, so that separation can be generated, and the protective performance is reduced on the contrary.
In one embodiment of the invention, the cross-linked starch comprises glutaraldehyde cross-linked starch, phosphorus oxychloride cross-linked starch, sodium trimetaphosphate cross-linked starch, adipic acid cross-linked starch, or hexametaphosphate cross-linked starch.
In one embodiment of the present invention, the Shear Thickening Gel (STG) is a protective material synthesized by reacting polydimethylsiloxane and boric acid at an elevated temperature.
In one embodiment of the present invention, the mass ratio of polydimethylsiloxane to boric acid is (10-100): 1.
It is a second object of the present invention to provide a method of improving the cold flow properties of a shear thickening elastomer by adding cross-linked starch as a filler to the shear thickening elastomer to improve the cold flow properties of the shear thickening elastomer.
In one embodiment of the invention, the cross-linked starch comprises glutaraldehyde cross-linked starch, phosphorus oxychloride cross-linked starch, sodium trimetaphosphate cross-linked starch, adipic acid cross-linked starch, or hexametaphosphate cross-linked starch.
The third purpose of the invention is to provide a method for preparing the shear thickening elastomer, which comprises the steps of uniformly mixing the shear thickening rubber, the silicon rubber, the glutaraldehyde crosslinked starch and the benzoyl peroxide, and vulcanizing the mixture for 10 to 20 minutes at 80 to 120 ℃ and 10 to 30Mpa to prepare the shear thickening elastomer. The silicon rubber and the benzoyl peroxide are respectively used as a vulcanizing agent and a high-molecular polymerization initiator, and are mainly used for vulcanizing at high temperature and high pressure to play a skeleton role and support the shear thickening rubber to lose cold flow property.
In one embodiment of the invention, the shear thickening rubber is 20-80 parts by mass, the silicon rubber is 20-80 parts by mass, the glutaraldehyde crosslinking starch is 2.5-120 parts by mass, and the benzoyl peroxide is 1 part by mass.
In one embodiment of the invention, the polydimethylsiloxane is polydimethylsiloxane with the viscosity of 500-20000 cst, the silicone rubber is 40-85 ten thousand molecular weight silicone rubber, and the diameter of the glutaraldehyde crosslinked starch is 5-100 μm.
In one embodiment of the present invention, the preparation method of the crosslinked starch reinforced composite shear thickening elastomer comprises the following steps:
(1) preparing glutaraldehyde crosslinked starch: taking 100 parts of oven-dried starch, adding 100-200 parts of deionized water, and stirring and dissolving to prepare starch milk; and adding 2-30 parts of 50% glutaraldehyde into the starch milk, and uniformly stirring. Mechanically stirring for 3-5 hours under the condition of heating in water bath at 30-50 ℃ to obtain uniform starch milk, carrying out vacuum filtration on the obtained starch milk, washing with cold water for 2-3 times, and drying at 50 ℃ to obtain a finished product of glutaraldehyde crosslinked starch;
(2) preparing a shear thickening gum: dehydrating boric acid at 140-180 ℃ for 2 hours, then adding boric acid into polydimethylsiloxane, and mechanically stirring and mixing for 1-3 hours at 160-210 ℃ to obtain shear thickening glue;
(3) preparation of shear thickening elastomer: adding the shear thickening rubber obtained in the step (1), silicon rubber, glutaraldehyde crosslinked starch and benzoyl peroxide into an internal mixer according to a proportion and uniformly mixing; pressing the obtained mixture into an aluminum alloy die with a customized size, and vulcanizing for 10-20 minutes at 80-120 ℃ under the condition of 10-30Mpa to obtain the crosslinked starch reinforced composite shear thickening elastomer.
In one embodiment of the present invention, the weight ratio of the polydimethylsiloxane to the boric acid in the step (2) is 10 to 100: 1.
in one embodiment of the invention, the mass ratio of the shear thickening glue, the silicone rubber, the glutaraldehyde crosslinked starch and the benzoyl peroxide in the step (3) is (20-80): (20-80): (2.5-120): 1.
in one embodiment of the invention, the internal mixer in the step (3) is operated at a temperature of 20-70 ℃.
It is a fourth object of the present invention to provide a shear thickening elastomer prepared by the above method.
The fifth purpose of the invention is to provide the application of the cross-linked starch reinforced composite shear thickening glue or shear thickening elastomer in the aspects of protective materials, damping materials and vibration reduction of precision instruments.
The sixth purpose of the invention is to provide a stab-resistant fabric, which is prepared by dissolving the shear thickening elastomer in a solvent, and then soaking the fabric in a solution containing the shear thickening elastomer for ultrasonic vibration treatment to obtain the stab-resistant fabric.
In one embodiment of the invention, the preparation method of the anti-blocking fabric is that the cross-linked starch reinforced composite shear thickening glue is prepared according to the following steps of 1: 5, soaking the fabric to be treated in the solution, treating the fabric by using ultrasonic waves to prevent starch from settling, taking out the fabric after 2 hours, and placing the fabric in an oven at 60 ℃ for drying for 24 hours to obtain the required fabric.
The invention also provides a protective material, which is prepared by compounding the crosslinked starch reinforced composite shear thickening glue or the shear thickening elastomer as a core material and a high-performance fiber fabric as a surface layer.
The invention has the beneficial effects that:
the dispersion used does not use conventional inorganic substances but rather crosslinked starch having a large number of reactive hydroxyl groups on the surface. The glutaraldehyde crosslinked starch has the characteristics of low toxic action, stable character, moderate reaction speed, easy control and the like, is low in price, and can generate a grafting reaction with the silicone oil in the preparation process of the shear thickening glue, and the molecular chain of the silicone oil is mainly grafted on the surface of the crosslinked starch. When external force is applied, long-chain macromolecules in the shear thickening rubber of the components of the shear thickening elastomer not only rub against adjacent long-chain macromolecules to dissipate energy and break B-O dynamic cross-linking bonds to absorb energy, but also can transmit force to a macromolecule long chain reacting with the long-chain macromolecules through the cross-linking points between the silicone oil and the starch. The cross-linked starch has good mechanical properties of enhancing the elastic modulus, the initial strength, the yield stress and the like of the composite shear thickening gel. By adopting a polymer network composite concept, the silicone rubber and the prepared shear thickening rubber are blended and further vulcanized, so that the original shear thickening characteristic is maintained, a shear thickening elastomer is endowed with higher initial elastic modulus and better elastic recovery capability, and the problem of cold flow property of the shear thickening rubber is solved.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of example 3 of the present invention.
FIG. 2 shows the X-ray photoelectron spectroscopy (XPS) broad spectra of the cross-linked starch-reinforced composite shear thickening gum of example 1, the cross-linked starch of step (1) of example 1, and the shear thickening gum of step (2) of example 1.
FIG. 3 is an XPS narrow spectrum of the cross-linked starch reinforced composite shear thickening gum Si2p of example 1.
FIG. 4 is an XPS narrow spectrum of cross-linked starch reinforced composite shear thickening gum C1s of example 1.
FIG. 5 is an XPS narrow spectrum of cross-linked starch reinforced composite shear thickening gum O1s of example 1.
FIG. 6 is a Fourier infrared spectrum of the cross-linked starch reinforced composite shear thickening gum of example 1, the cross-linked starch of step (1) of example 1, and the shear thickening gum of step (2) of example 1.
FIG. 7 is a hysteresis graph of each example and comparative example.
FIG. 8 is a stress-strain diagram for each example and comparative example.
Fig. 9 is a polarization diagram of example 5.
Fig. 10 is a polarization diagram of comparative example 3.
FIG. 11 is a morphology chart of shear thickening gels, wherein a, b, c, d, e, f correspond to the morphology change due to self-rheology of comparative example 4, comparative example 5, comparative example 6, example 1, example 2d, example 3, respectively, molded to an initial state of 10mm × 10mm × 30mm (top) and left to stand for 2h (bottom).
Detailed Description
The following description is of preferred embodiments of the present invention, and it should be understood that the embodiments are for better explaining the present invention, but not limiting the manufacturing method illustrated by the present invention.
1. Method for testing elastic modulus:
the stress and strain dependence of the samples was measured using a rotational rheometer in the set-up mode as strain-scan mode, using a PP25 type flat plate jig with a pitch of 1mm and a set temperature of 20 ℃. The experimental parameters were set to a fixed shear rate of 1rad/s, strain rate 0.01% to 20%. The shear stress and the shear strain show a certain positive correlation linear relationship in a certain strain range, which shows that all samples have linear viscoelasticity under a lower shear strain rate. When the shear strain rate is higher than a certain value, the viscosity of the sample is too high, and slippage with the upper plate of the rheometer can occur. At the same time the sample will also run out between the rheometer jaws, resulting in subsequent data with neither linear nor plateau. Therefore, for the convenience of calculation, the stress of each sample at the strain rate of 16.7% is selected and calculated based on the linear region in which each sample is located.
2. The hysteresis curve test method comprises the following steps:
the hysteresis curve of the sample was determined using a rotational rheometer with a large oscillation mode set, a fixed excitation frequency of 1Hz, a selected shear strain of 2.5%. The phenomenon that deformation lags behind changes in external force under the action of alternating stress is called hysteresis, and energy is consumed when the hysteresis occurs, called mechanical loss, also called internal loss. The larger the area enclosed by the hysteresis curve, the stronger its dissipation performance for energy. After origin plotted the hysteresis curve, the relative value of the closed curve was calculated using an integration tool with the area enclosed by the pure shear thickening gel curve being 100%.
3. X-ray photoelectron spectroscopy:
and (3) mixing the cross-linked starch reinforced composite shear thickening glue according to the weight ratio of 1: 10 in ethyl acetate, the solution was sprayed on a glass cover slip and the characteristic binding energy of C, O, Si element was determined using XPS.
4. A polarizing microscope:
the polarizing cross of the sample was observed using a polarizing microscope at a magnification of 200.
5. And (3) impact resistance test:
the performance of the drop weight testing machine on shearing thickening glue is that the impact energy is 45J, the diameter of a punch is 16mm, the weight of a hammer head is 5kg, and an impact clamp is a circular clamp with the diameter of 76 mm. And recording the maximum load and the energy absorption coefficient of the crosslinked starch reinforced composite shear thickening elastomer and the stab-resistant fabric when the crosslinked starch reinforced composite shear thickening elastomer and the stab-resistant fabric are impacted to determine the impact resistance of the sample.
Example 1: crosslinked starch reinforced composite shear thickening glue
A preparation method of a cross-linked starch reinforced composite shear thickening gum comprises the following steps:
(1) taking 100 parts of oven-dried starch, adding 100 parts of deionized water, stirring and dissolving to prepare the starch milk. And adding 10 parts of 50% glutaraldehyde into the starch milk, and uniformly stirring. Mechanically stirring for 5 hours under the condition of heating in water bath at 40 ℃ to obtain uniform starch milk. And carrying out vacuum filtration on the obtained starch milk, washing the starch milk for 2 to 3 times by cold water, and drying the starch milk at 50 ℃ to obtain a finished product of the glutaraldehyde crosslinked starch.
(2) Dehydrating boric acid at 160 ℃ for 2 hours, then adding 1 part of boric acid into 80 parts of 2000cst polydimethylsiloxane, and mechanically stirring and mixing for 2 hours at 160 ℃ to obtain shear thickening glue;
(3) glutaraldehyde cross-linked starch and shear thickening gum 10: 90 percent of the mixture is added into an internal mixer to be mixed evenly at the temperature of 50 ℃. And preparing the cross-linked starch reinforced composite shear thickening glue. The XPS broad spectrum and the element narrow spectrum are shown in figures 2, 3, 4 and 5 after being tested.
FIG. 2 shows XPS broad spectra of cross-linked starch-reinforced composite shear thickening gum, cross-linked starch, shear thickening gum.
FIG. 3 is an XPS narrow spectrum of cross-linked starch reinforced composite shear thickening gum Si2p, wherein 103.2eV, 102.4eV, 102.0eV represent Si-O-Si, Si-O-C, and Si-C-H groups, wherein Si-O-Si, Si-C-H are self-carried by PDMS, and Si-O-C is generated during heating.
FIG. 4 shows an XPS narrow spectrum of a crosslinked starch reinforced composite shear thickening gel C1s, wherein 284.6eV, 285.2eV and 286.2eV near the peak of C1s represent C-C-H, C-Si-O, C-O-Si, respectively.
FIG. 5 is an XPS narrow spectrum of cross-linked starch reinforced composite shear thickening gel O1s, where the O1s peak can be divided into Si-O-Si, C-O-C and Si-O-C groups with electron volts of 532.5eV, 533.0eV and 533.4 eV. Together with FIGS. 2 and 3, the formation of new covalent bonds between the crosslinked starch and the shear thickening gum is illustrated.
As shown in FIG. 6, 1340cm is obtained by Fourier infrared spectroscopy of the crosslinked starch reinforced composite shear thickening glue, the crosslinked starch and the shear thickening glue-1The weak absorption peak of (a) is due to the ` B-O ` vibrational peak due to boric acid. The main shear thickening characteristics of the crosslinked starch reinforced composite shear thickening elastomer are derived from dynamic 'B-O' bonds of the shear thickening adhesive and a grafting reaction formed by starch and silicone oil in a heating process, and the shear thickening adhesive is more convenient and visual in test, so that the superiority of the starch reinforced composite shear thickening adhesive can be visually known by testing the shear thickening adhesives with different fillers.
The cold flow test in fig. 11 shows that, for example 1, a low starch content also reduces the cold flow of the shear thickening gum, and that the sample has a certain shape after 2 h.
Example 2:
the crosslinked starch-reinforced composite shear thickening gum was prepared by referring to the method of example 1, except that the mass ratio of the glutaraldehyde crosslinked starch to the shear thickening gum in example 1 was adjusted to 2:8, 3:7, 4:6, 5:5, and 6:4, and the other conditions were the same as in example 1. For convenience of subsequent comparisons, they were numbered as example 2a, example 2b, example 2c, example 2d, example 2 e.
TABLE 1
And (3) determining the modulus and the energy absorption performance of the starch reinforced composite shear thickening gel by using a stress strain mode and a large oscillation mode of a rheometer. The larger the modulus of the sample is, the higher the stress can be obtained when the sample is subjected to external force, and therefore the better protection effect can be achieved. The larger the area enclosed by the hysteresis curve, the greater the energy dissipation capacity of the hysteresis curve, and accordingly the more energy can be dissipated when the object is impacted to ensure that the protected object is subjected to lower energy. The data in table 1 correspond to fig. 7 and 8. It can be seen that, within a certain range, the relative area of the shear modulus and the hysteresis curve of the crosslinked starch reinforced composite shear thickening gel is continuously increased along with the increase of the starch content, and when the mass of the starch reaches 50 wt%, the highest point is reached. Mainly because when the starch content is too high, the shear thickening gum as the continuous phase is less continuous when subjected to external force, and is more likely to crack.
As shown in fig. 11, sample e is example 2d, the cold flow property is caused by the slippage of the macromolecules, and the high starch content can fix the macromolecules inside to some extent, but cannot completely prevent the slippage of the macromolecules. The best cold flow resistance was found in the unvulcanized samples.
Example 3:
a preparation method of a crosslinked starch reinforced composite shear thickening elastomer comprises the following steps:
(1) preparing glutaraldehyde crosslinked starch: taking 100 parts of oven-dried starch, adding 100 parts of deionized water, stirring and dissolving to prepare the starch milk. And adding 10 parts of 50% glutaraldehyde into the starch milk, and uniformly stirring. Mechanically stirring for 5 hours under the condition of heating in water bath at 40 ℃ to obtain uniform starch milk. And carrying out vacuum filtration on the obtained starch milk, washing the starch milk for 2 to 3 times by cold water, and drying the starch milk at 50 ℃ to obtain a finished product of the glutaraldehyde crosslinked starch.
(2) Preparing a shear thickening gum: dehydrating boric acid at 160 ℃ for 2 hours, then adding 1 part of boric acid into 80 parts of 2000cst polydimethylsiloxane, and mechanically stirring and mixing for 3 hours at 160 ℃ to obtain shear thickening glue;
(3) preparation of shear thickening elastomer: and (3) mixing glutaraldehyde crosslinked starch obtained in the step (1), the shear thickening gum obtained in the step (2), 80-ten-thousand molecular weight silicone rubber and benzoyl peroxide according to the weight ratio of 30: 35: 35: 1 is added into an internal mixer to be mixed evenly at the temperature of 50 ℃. Pressing the obtained mixture into an aluminum alloy die with a customized size, and vulcanizing for 15 minutes at 100 ℃ and 20Mpa to obtain the crosslinked starch reinforced composite shear thickening elastomer.
From table 2 it can be seen that example 3, without the support of the substrate, collapsed more easily and absorbed energy less strongly than with kevlar fabric. But has a greater increase in energy absorption capacity than comparative example 7, mainly due to the mechanical reinforcement of the starch for the shear thickening elastomer.
As shown in fig. 11, sample f is example 3, and due to the existence of the silicone rubber component, the internal macromolecules can not slip at all, thereby solving the problem of cold flowability of the shear thickening rubber in the using process.
TABLE 2
Example 4:
a preparation method of a crosslinked starch reinforced composite shear thickening elastomer comprises the following steps:
(1) taking 100 parts of oven-dried starch, adding 100 parts of deionized water, stirring and dissolving to prepare the starch milk. And adding 30 parts of 50% glutaraldehyde into the starch milk, and uniformly stirring. Mechanically stirring for 3 hours under the condition of heating in water bath at 50 ℃ to obtain uniform starch milk. And carrying out vacuum filtration on the obtained starch milk, washing the starch milk for 2 to 3 times by cold water, and drying the starch milk at 50 ℃ to obtain a finished product of the glutaraldehyde crosslinked starch.
(2) Dehydrating boric acid at 180 ℃ for 1 hour, then adding 1 part of boric acid into 80 parts of 2000cst polydimethylsiloxane, and mechanically stirring and mixing for 1 hour at 210 ℃ to obtain a shear thickening gel;
(3) and (3) mixing glutaraldehyde crosslinked starch obtained in the step (1), the shear thickening gum obtained in the step (2), 80-ten-thousand molecular weight silicone rubber and benzoyl peroxide according to the weight ratio of 30: 35: 35: 1 is added into an internal mixer to be mixed evenly at the temperature of 50 ℃. Pressing the obtained mixture into an aluminum alloy die with a customized size, and vulcanizing for 15 minutes at 100 ℃ and 20Mpa to obtain the crosslinked starch reinforced composite shear thickening elastomer.
Example 5:
a crosslinked starch-reinforced composite shear thickening gum was prepared by reference to the method of example 2a, except that the starch of example 2a was changed to a commercially available formaldehyde crosslinked starch, and the other conditions were the same as in example 2 a. As shown by the results of the polarizing microscope in FIG. 9, the prepared sample had no significant phenomena of starch pyrolysis and dehydration, and still had clear and significant polarizing crosses. This indicates that the crosslinking reaction enhances the resistance of the starch to high pressure and heat.
Example 6: anti-stab fabric
A protective material is prepared by taking Kevlar fabric as a raw material, taking 200g of the crosslinked starch reinforced composite shear thickening glue prepared in the embodiment 2a according to the weight ratio of 1: 5 in proportion by weight is dissolved in ethyl acetate, fabric prepared by Kevlar fiber is cut into a square of 200mm multiplied by 200mm, then the fabric is soaked in the solution and treated by ultrasonic wave to prevent starch from settling, and the fabric is taken out after 2 hours and is placed in a 60 ℃ oven for drying for 24 hours to obtain the required fabric. The data in table 2 show that the single-layer Kevlar fabric treated by the crosslinked starch reinforced composite shear thickening glue can greatly enhance the energy dissipation capability of the fabric. The crosslinked starch reinforced composite shear thickening glue increases the friction force between Kevlar fibers, when the composite material is subjected to an external force, the fibers are not easy to draw out from the fabric, and the force can be more uniformly dispersed to the whole, so that the maximum impact load of the composite material is enhanced.
Example 7: protective material
A protective material is prepared by taking two layers of 200mm x 200mm Kevlar as surface materials, preparing a cross-linked starch reinforced composite shear thickening elastomer in the embodiment 3 into a shape of 180mm x 3mm in a mold, using an adhesive to bond three layers of raw materials as a core material, and fixing stitches by using a sewing machine in a cross manner to obtain the required fabric. The data in table 2 show that the double-layer Kevlar fabric and the crosslinked starch reinforced composite shear thickening elastomer solve the problem that the crosslinked starch reinforced composite shear thickening elastomer collapses under external force, and the stress becomes hard instantly, so that the stress can be completely diffused to the whole sample.
Comparative example 1:
CaCO (calcium carbonate)3A preparation method of a reinforced composite shear thickening gum comprises the following steps:
(1) dehydrating boric acid at 180 ℃ for 1 hour, then adding 1 part of boric acid into 80 parts of 2000cst polydimethylsiloxane, and mechanically stirring and mixing for 2 hours at 160 ℃ to obtain a shear thickening gel;
(2) shearing thickening glue and CaCO obtained in the step (1)3According to the following steps of 20: 80 proportion is added into an internal mixer to be mixed evenly at 50 ℃ to obtain CaCO3And (3) reinforcing the composite shear thickening glue. As can be seen from fig. 7 and table 3, the results show: CaCO3The energy dissipation capacity of the reinforced composite shear thickening glue is higher than that of the shear thickening glue and lower than that of the cross-linked starch reinforced composite shear thickening glue, which shows that the energy dissipation capacity of the shear thickening glue is enhanced to a certain extent but lower than that of the cross-linked starch by the inorganic particles. The inorganic particles generate stress concentration to be beneficial to absorbing energy, and the inorganic particles are added to be beneficial to internal chain entanglement to improve the nonlinear characteristic of the material, but the surface of the inorganic particles has no group capable of reacting with the shear thickening adhesive, and the interaction force is limited, so that the situation of phase separation between a dispersed phase and a continuous phase can be generated when the content reaches a lower degree, and the force is appliedThe chemical properties are much lower than those of samples with the same mass fraction of starch as filler.
Comparative example 2:
SiO (silicon dioxide)2A method of preparing a reinforced composite shear thickening elastomer, the method comprising the steps of:
(1) dehydrating boric acid at 180 ℃ for 1 hour, then adding 1 part of boric acid into 80 parts of 2000cst polydimethylsiloxane, and mechanically stirring and mixing for 2 hours at 160 ℃ to obtain a shear thickening gel;
(2) shearing thickening glue and SiO obtained in the step (1)2According to the following steps of 20: 80 percent of the mixture is added into an internal mixer to be mixed evenly at 50 ℃ to obtain SiO2A reinforced composite shear thickening elastomer. As can be seen from FIG. 7 and Table 3, the results are shown together with CaCO3The results are similar.
Comparative example 3:
a preparation method of a common starch reinforced composite shear thickening gum comprises the following steps:
(1) dehydrating boric acid at 160 ℃ for 1 hour, then adding 1 part of boric acid into 80 parts of 2000cst polydimethylsiloxane, and mechanically stirring and mixing for 2 hours at 160 ℃ to obtain a shear thickening gel;
(2) and (2) mixing the shear thickening glue and the starch obtained in the step (1) according to the weight ratio of 20: adding the starch in the proportion of 80 into an internal mixer, and uniformly mixing at 50 ℃ to obtain the starch reinforced composite shear thickening rubber. As can be seen from fig. 10, the results show: under a polarizing microscope, comparing with the cross-linked starch of example 5 in FIG. 9, the polarizing cross of the ordinary starch in the sample becomes blurred or even disappears under high heat and high pressure, which indicates that the starch granule is destroyed by heat without cross-linking. From the rheometer data, the loss capacity to external forces is reduced to some extent.
Comparative example 4:
a method of making a shear thickening gum, the method comprising the steps of:
boric acid was dehydrated at 180 ℃ for 1 hour, then 1 part boric acid was added to 80 parts 2000cst polydimethylsiloxane, and mechanically stirred and mixed at 160 ℃ for 2 hours to obtain a shear thickening gel. Compared with example 2d, the shear thickening gum alone has a lower modulus and a poor energy dissipation capacity, which indicates that the addition of cross-linked starch can greatly enhance the instant stiffening and energy dissipation capacity of the shear thickening gum under high load.
As shown in FIG. 11, sample a is comparative example 4, and compared with example 3, the shear thickening adhesive alone has no shape retention property for a long time, has strong cold flow property, and can not maintain the original shape after 2 hours. The rheological property of the starch and the silicon rubber can be solved by adding and vulcanizing the starch and the silicon rubber.
Comparative example 5:
the shear thickening gel, CaCO, of comparative example 1 (2) with the remaining steps unchanged3The ratio of the organic solvent to the organic solvent is 50: 50. As is clear from FIGS. 7, 8 and Table 3, the CaCO content was higher than that of example 2d3The levels are not as good as starch for shear thickening gels with an order of magnitude of modulus and energy dissipation enhancement capability.
As shown in FIG. 11, sample b is comparative example 5, which has a higher CaCO content than example 33Nor to reduce the cold flow properties of the shear-thickening gum to some extent.
Comparative example 6:
the other steps are not changed, and the shear thickening gel and SiO of the (2) in the comparative example 2 are added2The proportion is as follows 50: 50. As can be seen from FIG. 7 and Table 3, the results are shown together with CaCO3Similarly.
As shown in FIG. 11, sample c is comparative example 6, which has a higher SiO content than example 32Nor to reduce the cold flow properties of the shear-thickening gum to some extent.
TABLE 3
As can be seen from fig. 7, fig. 8 and table 3, the hysteresis curve area surrounded by the curves of the samples using starch as the filler is far larger than that of the reinforced composite shear thickening glue of CaCO3 and SiO2 no matter the addition amount of the filler particles is 20 wt% or 50 wt%. This is mainly due to the fine wrinkles on the surface of the starch particles and the grafting reaction of the starch with the silicone oil (polydimethylsiloxane) in the shear thickening gum during heating. Therefore, preferably, the mass ratio of cross-linked starch to shear thickening gum is 1: 1.
comparative example 7:
a method of preparing a shear thickening elastomer, the method comprising the steps of:
(1) preparing a shear thickening gum: dehydrating boric acid at 160 ℃ for 2 hours, then adding 1 part of boric acid into 80 parts of 2000cst polydimethylsiloxane, and mechanically stirring and mixing for 3 hours at 160 ℃ to obtain shear thickening glue;
(2) preparation of shear thickening elastomer: mixing the shear thickening gel obtained in the step (2) obtained in the step (1), 80 ten thousand molecular weight silicon rubber and benzoyl peroxide according to the weight ratio of 35: 35: 1 is added into an internal mixer to be mixed evenly at the temperature of 50 ℃. Pressing the obtained mixture into an aluminum alloy die with a customized size, and vulcanizing for 15 minutes at 100 ℃ and 20Mpa to obtain the cross-shear thickening elastomer. As can be seen from the data in Table 2, the shear thickening elastomer alone has less than the maximum impact load and energy absorption capacity compared to example 3, which indicates that the addition of cross-linked starch can greatly enhance the instant hardening and energy dissipation capacity of the shear thickening gum under high load.
Comparative example 8:
the other steps are not changed, the crosslinked starch reinforced composite shear thickening glue in the embodiment 6 is replaced by the shear thickening glue in the comparative example 4, and the other steps are not changed. As can be seen from the data in table 2, compared with example 6, it is known that the effect of enhancing the friction force between fibers by shearing the thickening gum alone is limited, and no significant enhancing effect is obtained.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (3)
1. A crosslinked starch-reinforced composite shear thickening gum, wherein the crosslinked starch-reinforced composite shear thickening gum comprises a crosslinked starch and a shear thickening gum; the mass ratio of the cross-linked starch to the shear thickening glue is (1-6): (4-9); the cross-linked starch is glutaraldehyde cross-linked starch; the shear thickening gel is a protective material synthesized by polydimethylsiloxane and boric acid through reaction at high temperature; the mass ratio of the polydimethylsiloxane to the boric acid is (10-100): 1.
2. The use of the crosslinked starch reinforced composite shear thickening gum of claim 1 in protective materials, damping materials, and vibration damping for precision instruments.
3. The protective material is characterized in that the protective material is obtained by compounding the crosslinked starch reinforced composite shear thickening glue as claimed in claim 1 as a core material and a high-performance fiber fabric as a surface layer.
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