CN114350180A - Mechanical activation nano-modified heavy calcium carbonate and preparation method thereof - Google Patents
Mechanical activation nano-modified heavy calcium carbonate and preparation method thereof Download PDFInfo
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 434
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 218
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000004137 mechanical activation Methods 0.000 title abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 73
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims abstract description 32
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims abstract description 32
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- 238000001035 drying Methods 0.000 claims abstract description 21
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Abstract
The invention discloses a preparation method of mechanical activation nano-modified heavy calcium carbonate, which comprises the following steps: s1, placing a heavy calcium carbonate sample in a forced air drying oven for drying; s2, adding the dried heavy calcium carbonate sample and sodium polyacrylate into a grinding tank for grinding, and then adding nano calcium carbonate for continuous grinding to obtain a primary product; and S3, obtaining the mechanically activated nano-modified heavy calcium carbonate by sieving after the reaction is finished. According to the invention, the surface of the heavy calcium carbonate powder is coated with a layer of nano calcium carbonate, sharp edges and corners on the surface of heavy calcium carbonate particles can be passivated by the nano particle layer, and the smooth cleavage surface of the heavy calcium carbonate particles is also rough due to the existence of the nano structure on the surface of the particles. The composite calcium carbonate particles filled into the matrix material can relieve the problem of local stress concentration inside the composite material caused by sharp edges and flat crystal cleavage surfaces, thereby improving the mechanical property of the product and improving the use function and value of the heavy calcium carbonate.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of heavy calcium carbonate modification processing, in particular to a mechanical activation nano-modified heavy calcium carbonate and a preparation method thereof.
[ background of the invention ]
Although the surface characteristics of the existing calcium carbonate organic modification method can be changed, the surface is changed from hydrophilic to oleophilic, so that the existing calcium carbonate organic modification method has better compatibility with organic materials. However, the calcium carbonate particles formed during the ultrafine grinding process are microscopically similar to cullet, with many sharp edges and smooth surfaces formed during grinding. Research on the micro fracture mechanics of the composite material shows that the sharp edges are always stress concentration points in the material, and cracks are always initiated from the sharp edges. In the extrusion process of plastics, the sharp edges and corners of calcium carbonate particles have great abrasion on the screw of the plastic extruder. The smooth surface of the calcium carbonate particles makes it difficult to form effective bonds and tight entanglements with the macromolecules of the polymeric material. The traditional surface organic modification method cannot solve the defects formed in the process of ultrafine grinding of particles, so that the performance of the polymer material filled with calcium carbonate is limited to a great extent, and the use effect of the calcium carbonate is directly influenced.
[ summary of the invention ]
Aiming at the problems, the invention provides the heavy calcium carbonate modified by the mechanical activation nanometer and the preparation method thereof, the processing technology wraps the nanometer calcium carbonate on the surface of the heavy calcium carbonate, thereby overcoming the problems existing when the heavy calcium carbonate is filled with polymer materials and leading the heavy calcium carbonate to become a good filling material; the method has the advantages of simple process, low production cost, convenient operation and suitability for large-scale production.
In order to realize the problems, the invention adopts the following technical scheme:
a preparation method of mechanically activated nano-modified heavy calcium carbonate comprises the following steps:
s1, placing a heavy calcium carbonate sample in a forced air drying oven for drying;
s2, adding the dried heavy calcium carbonate sample and sodium polyacrylate into a grinding tank for grinding, and then adding nano calcium carbonate for continuous grinding to obtain a primary product;
and S3, obtaining the mechanically activated nano-modified heavy calcium carbonate by sieving after the reaction is finished.
Preferably, the temperature for drying in step S1 is 90 ℃.
Preferably, the drying time is 1 h.
Preferably, the sample of ground calcium carbonate in step S2 is 50 g.
Preferably, the amount of the sodium polyacrylate used in step S2 is 0.2-1.0% of the weight of the ground calcium carbonate sample.
Preferably, in the step S2, the dried ground calcium carbonate sample and the sodium polyacrylate are added into the grinding tank for grinding for 10-50 min.
Preferably, the amount of the nano calcium carbonate in step S2 is 5-25% (wt) of the weight of the ground calcium carbonate sample.
Preferably, the grinding time for adding the nano calcium carbonate in the step S2 is 10-50 min.
Preferably, the rotation speed during the grinding in the step S2 is 250 to 450 r/min.
The invention also provides a heavy calcium carbonate nano-modified by mechanical activation, which is used as a filler and filled in polybutylene terephthalate (PBT) resin, and the addition amount is 10-30%.
Compared with the prior art, the invention has the following technical advantages:
firstly, a layer of nano calcium carbonate is coated on the surface of heavy calcium carbonate powder, and the characteristics of nano particles can be utilized to realize the nano particle combination of the composite particles at the material interface during filling application, which is equivalent to improving the use function and value of the heavy calcium carbonate.
Secondly, through surface nano-modification, sharp edges and corners on the surface of heavy calcium carbonate particles can be passivated by the nano-particle layer, and the smooth and flat cleavage surface of the heavy calcium carbonate particles is also rough due to the existence of the nano-structure on the surface of the particles. The composite calcium carbonate particles filled into the matrix material can relieve the problem of local stress concentration inside the composite material caused by sharp edges and flat crystal cleavage surfaces, thereby improving the mechanical property of the product.
Thirdly, the technology of the invention correspondingly solves the problems that the nano calcium carbonate particles are difficult to disperse when directly applied.
Fourthly, in the process, the optimal dosage of the sodium polyacrylate is 0.8 percent of the mass of the heavy calcium carbonate sample, and the optimal dosage of the nano calcium carbonate is 20 percent of the mass of the heavy calcium carbonate sample; the prepared mechanical activation nano-modified heavy calcium carbonate is used as a filler and filled in polybutylene terephthalate (PBT) resin, the optimal addition amount is 20 percent, the production cost can be guided and controlled, and the optimal benefit can be obtained.
Fifthly, the method has the advantages of simple process, low production cost, convenient operation, suitability for large-scale production and wide popularization and application.
[ description of the drawings ]
FIG. 1 is a photograph of a non-nano-modified ground calcium carbonate obtained by scanning electron microscopy at a magnification of 5 k;
FIG. 2 is a scanning electron micrograph of the activated nano-modified heavy calcium carbonate prepared in example 4 at a magnification of 10 k;
FIG. 3 is a 24 k-fold scanning electron micrograph of the activated nano-modified ground calcium carbonate prepared in example 4;
fig. 4 is the XRD pattern of activated nano-modified ground calcium carbonate prepared in example 4.
[ detailed description ] embodiments
The invention will be better understood and explained by the following examples, which do not limit the scope of the invention.
Example 1
A preparation method of mechanically activated nano-modified heavy calcium carbonate comprises the following steps:
s1, accurately weighing a certain amount of heavy calcium carbonate sample, and drying the heavy calcium carbonate sample in a 90 ℃ forced air drying oven for 1 h;
s2, weighing 50g of the dried ground calcium carbonate sample, adding 0.8 wt% of sodium polyacrylate, uniformly mixing, adding into a grinding tank, and grinding for 30 min; then adding 5 wt% of nano calcium carbonate and continuously grinding for 30min to obtain a primary product, wherein the grinding rotating speeds of the two times are both 400 r/min;
and S3, obtaining the mechanically activated nano-modified heavy calcium carbonate by sieving after the reaction is finished.
Example 2
A preparation method of mechanically activated nano-modified heavy calcium carbonate comprises the following steps:
s1, accurately weighing a certain amount of heavy calcium carbonate sample, and drying the heavy calcium carbonate sample in a 90 ℃ forced air drying oven for 1 h;
s2, weighing 50g of the dried ground calcium carbonate sample, adding 0.8 wt% of sodium polyacrylate, uniformly mixing, adding into a grinding tank, and grinding for 30 min; then adding 10 wt% of nano calcium carbonate and continuously grinding for 30min to obtain a primary product, wherein the grinding rotating speeds of the two times are both 400 r/min;
and S3, obtaining the mechanically activated nano-modified heavy calcium carbonate by sieving after the reaction is finished.
Example 3
A preparation method of mechanically activated nano-modified heavy calcium carbonate comprises the following steps:
s1, accurately weighing a certain amount of heavy calcium carbonate sample, and drying the heavy calcium carbonate sample in a 90 ℃ forced air drying oven for 1 h;
s2, weighing 50g of the dried ground calcium carbonate sample, adding 0.8 wt% of sodium polyacrylate, uniformly mixing, adding into a grinding tank, and grinding for 30 min; then adding 15 wt% of nano calcium carbonate and continuously grinding for 30min to obtain a primary product, wherein the grinding rotating speeds of the two times are both 400 r/min;
and S3, obtaining the mechanically activated nano-modified heavy calcium carbonate by sieving after the reaction is finished.
Example 4
A preparation method of mechanically activated nano-modified heavy calcium carbonate comprises the following steps:
s1, accurately weighing a certain amount of heavy calcium carbonate sample, and drying the heavy calcium carbonate sample in a 90 ℃ forced air drying oven for 1 h;
s2, weighing 50g of the dried ground calcium carbonate sample, adding 0.8 wt% of sodium polyacrylate, uniformly mixing, adding into a grinding tank, and grinding for 30 min; then adding 20 wt% of nano calcium carbonate, and continuously grinding for 30min to obtain a primary product, wherein the grinding rotating speeds of the two times are both 400 r/min;
and S3, obtaining the mechanically activated nano-modified heavy calcium carbonate by sieving after the reaction is finished.
Example 5
A preparation method of mechanically activated nano-modified heavy calcium carbonate comprises the following steps:
s1, accurately weighing a certain amount of heavy calcium carbonate sample, and drying the heavy calcium carbonate sample in a 90 ℃ forced air drying oven for 1 h;
s2, weighing 50g of the dried ground calcium carbonate sample, adding 0.8 wt% of sodium polyacrylate, uniformly mixing, adding into a grinding tank, and grinding for 30 min; then adding 25 wt% of nano calcium carbonate, and continuously grinding for 30min to obtain a primary product, wherein the grinding rotating speeds of the two times are both 400 r/min;
and S3, obtaining the mechanically activated nano-modified heavy calcium carbonate by sieving after the reaction is finished.
Example 6
A preparation method of mechanically activated nano-modified heavy calcium carbonate comprises the following steps:
s1, accurately weighing a certain amount of heavy calcium carbonate sample, and drying the heavy calcium carbonate sample in a 90 ℃ forced air drying oven for 1 h;
s2, weighing 50g of the dried ground calcium carbonate sample, adding 0.8 wt% of sodium polyacrylate, uniformly mixing, adding into a grinding tank, and grinding for 10 min; then adding 20 wt% of nano calcium carbonate and continuously grinding for 10min to obtain a primary product, wherein the grinding rotating speeds of the two times are both 400 r/min;
and S3, obtaining the mechanically activated nano-modified heavy calcium carbonate by sieving after the reaction is finished.
Example 7
A preparation method of mechanically activated nano-modified heavy calcium carbonate comprises the following steps:
s1, accurately weighing a certain amount of heavy calcium carbonate sample, and drying the heavy calcium carbonate sample in a 90 ℃ forced air drying oven for 1 h;
s2, weighing 50g of the dried ground calcium carbonate sample, adding 0.8 wt% of sodium polyacrylate, uniformly mixing, adding into a grinding tank, and grinding for 50 min; then adding 20 wt% of nano calcium carbonate, and continuously grinding for 50min to obtain a primary product, wherein the grinding rotating speeds of the two times are both 400 r/min;
and S3, obtaining the mechanically activated nano-modified heavy calcium carbonate by sieving after the reaction is finished.
Example 8
A preparation method of mechanically activated nano-modified heavy calcium carbonate comprises the following steps:
s1, accurately weighing a certain amount of heavy calcium carbonate sample, and drying the heavy calcium carbonate sample in a 90 ℃ forced air drying oven for 1 h;
s2, weighing 50g of the dried heavy calcium carbonate sample, adding 0.2 wt% of sodium polyacrylate, uniformly mixing, adding into a grinding tank, and grinding for 30 min; then adding 20 wt% of nano calcium carbonate, and continuously grinding for 30min to obtain a primary product, wherein the grinding rotating speeds of the two times are both 400 r/min;
and S3, obtaining the mechanically activated nano-modified heavy calcium carbonate by sieving after the reaction is finished.
Example 9
A preparation method of mechanically activated nano-modified heavy calcium carbonate comprises the following steps:
s1, accurately weighing a certain amount of heavy calcium carbonate sample, and drying the heavy calcium carbonate sample in a 90 ℃ forced air drying oven for 1 h;
s2, weighing 50g of the dried heavy calcium carbonate sample, adding 0.4 wt% of sodium polyacrylate, uniformly mixing, adding into a grinding tank, and grinding for 30 min; then adding 20 wt% of nano calcium carbonate, and continuously grinding for 30min to obtain a primary product, wherein the grinding rotating speeds of the two times are both 400 r/min;
and S3, obtaining the mechanically activated nano-modified heavy calcium carbonate by sieving after the reaction is finished.
Example 10
A preparation method of mechanically activated nano-modified heavy calcium carbonate comprises the following steps:
s1, accurately weighing a certain amount of heavy calcium carbonate sample, and drying the heavy calcium carbonate sample in a 90 ℃ forced air drying oven for 1 h;
s2, weighing 50g of the dried heavy calcium carbonate sample, adding 0.6 wt% of sodium polyacrylate, uniformly mixing, adding into a grinding tank, and grinding for 30 min; then adding 20 wt% of nano calcium carbonate, and continuously grinding for 30min to obtain a primary product, wherein the grinding rotating speeds of the two times are both 400 r/min;
and S3, obtaining the mechanically activated nano-modified heavy calcium carbonate by sieving after the reaction is finished.
Example 11
A preparation method of mechanically activated nano-modified heavy calcium carbonate comprises the following steps:
s1, accurately weighing a certain amount of heavy calcium carbonate sample, and drying the heavy calcium carbonate sample in a 90 ℃ forced air drying oven for 1 h;
s2, weighing 50g of the dried heavy calcium carbonate sample, adding 1.0 wt% of sodium polyacrylate, uniformly mixing, adding into a grinding tank, and grinding for 30 min; then adding 20 wt% of nano calcium carbonate, and continuously grinding for 30min to obtain a primary product, wherein the grinding rotating speeds of the two times are both 400 r/min;
and S3, obtaining the mechanically activated nano-modified heavy calcium carbonate by sieving after the reaction is finished.
Example 12
A preparation method of mechanically activated nano-modified heavy calcium carbonate comprises the following steps:
s1, accurately weighing a certain amount of heavy calcium carbonate sample, and drying the heavy calcium carbonate sample in a 90 ℃ forced air drying oven for 1 h;
s2, weighing 50g of the dried heavy calcium carbonate sample, adding 1.0 wt% of sodium polyacrylate, uniformly mixing, adding into a grinding tank, and grinding for 30 min; then adding 20 wt% of nano calcium carbonate, and continuously grinding for 30min to obtain a primary product, wherein the grinding rotating speeds of the two times are both 250 r/min;
and S3, obtaining the mechanically activated nano-modified heavy calcium carbonate by sieving after the reaction is finished.
Example 13
A preparation method of mechanically activated nano-modified heavy calcium carbonate comprises the following steps:
s1, accurately weighing a certain amount of heavy calcium carbonate sample, and drying the heavy calcium carbonate sample in a 90 ℃ forced air drying oven for 1 h;
s2, weighing 50g of the dried heavy calcium carbonate sample, adding 1.0 wt% of sodium polyacrylate, uniformly mixing, adding into a grinding tank, and grinding for 30 min; then adding 20 wt% of nano calcium carbonate, and continuously grinding for 30min to obtain a primary product, wherein the grinding rotating speeds of the two times are both 450 r/min;
and S3, obtaining the mechanically activated nano-modified heavy calcium carbonate by sieving after the reaction is finished.
(1) The properties of the ground calcium carbonate sample dried in step S1, the nano calcium carbonate product prepared in a laboratory, and the nano-modified ground calcium carbonate product prepared in example 4 were measured, and the measurement results are shown in table 1:
TABLE 1
Note: in the table, the oil absorption values of heavy calcium carbonate, nano calcium carbonate and nano modified heavy calcium carbonate are all expressed by the activated results.
The method for self-making the nano calcium carbonate product in the laboratory comprises the following steps: stirring and digesting for 2 hours at the constant temperature of 80 ℃ with the weight ratio of water to calcium oxide of 5: 1; sieving the calcium hydroxide slurry obtained by digestion with a 200-mesh sieve, and removing large-particle impurities to obtain refined oxyhydrogenCalcium dissolving slurry; aging the obtained refined calcium hydroxide slurry at room temperature for 12h, and adjusting the calcium hydroxide slurry obtained by aging to the required concentration; before the carbonization reaction, 2 percent of glucose is added into the calcium hydroxide slurry, and the mixture is stirred to be uniformly mixed; adding refined calcium hydroxide slurry into a supergravity-micro interface carbonization reactor, adjusting the temperature of the carbonization initial reaction to be 30 ℃, and introducing CO2Detecting and recording the carbonization reaction process by using a pH meter and a conductivity meter in the carbonization reaction process; when the pH value of the slurry is reduced to 7, finishing the carbonization reaction; and centrifugally separating the obtained slurry, and drying the precipitated solid at the temperature of 80 ℃ for 12 hours to obtain the nano calcium carbonate product.
BET is specific surface area, the detection is carried out by using a specific surface analyzer ASAP 2420-4, the apparatus manufacturer is American Mike apparatus company, and the test conditions are as follows: the degassing time was 2h, the degassing temperature was 80 ℃, the analysis gas was nitrogen, and the equilibration time was 20 s.
The particle size distribution was measured using a static particle image analyser MORPHO1OGI G3S, the manufacturer of which is Marvin instruments Inc. of England
The method for measuring the oil absorption value comprises the following steps: weighing 5.00g of sample, placing the sample in a clean and dry beaker, gradually dripping dibutyl phthalate (DOP) by using a rubber head dropper, continuously stirring and grinding calcium carbonate powder particles by using a glass rod until all dispersed samples are wetted into a cluster without dispersion, stopping dripping dibutyl phthalate, recording the dosage of DOP to calculate the oil absorption value, repeating the experiment operation for three times, and calculating the average value.
Calculation of oil absorption value: x ═ m1/m*100
In the formula: x-oil absorption value, g (100g)-1；
m1-mass (g) of dibutyl phthalate added dropwise;
m-mass of sample (g).
The crystal form is detected by an X-ray diffractometer Rigaku D/MAX 2500V, and the test conditions are as follows: the step size is 0.03 degrees, the scanning speed is 10 degrees/min, and the diffraction angle range is 10 degrees to 80 degrees.
Wherein the electron micrograph of the heavy calcium carbonate sample is shown in figure 1; FIGS. 2 and 3 are the electron micrographs of the nano-modified heavy calcium carbonate product prepared in example 4 at different magnifications, and it can be seen from the electron micrographs that the heavy calcium carbonate surface is coated with a layer of nano-calcium carbonate and the coating effect is good; fig. 4 is the XRD pattern of the nano-modified heavy calcium carbonate product prepared in example 4, and it can be seen from fig. 4 that the main phase is still calcite, and no new diffraction peak appears.
From table 1 it can be found that: compared with the heavy calcium carbonate raw material, the oil absorption value of the heavy calcium carbonate particle product subjected to mechanical activation nano modification is improved, but is lower than the oil absorption value of the original nano calcium carbonate. Through grinding and surface nano-modification of the particles, the heavy calcium carbonate raw material is refined, simultaneously, the particle surface is roughened, the specific surface area is increased, and therefore, the oil absorption is increased, but compared with nano-calcium carbonate, the oil absorption value is lower, so that the modification difficulty of the calcium carbonate applied to the plastic additive is reduced, and the modification cost is greatly reduced.
(2) The effect of different sodium polyacrylate addition amounts on the BET of the nano-modified ground calcium carbonate is shown in table 2.
TABLE 2
In table 2 it can be found: with the increase of the addition amount of the sodium polyacrylate, BET of the nano-modified heavy calcium carbonate also increases; when the addition amount of the sodium polyacrylate is 0.8 percent by weight, the BET of the nano-modified heavy calcium carbonate can reach 14.48m2(ii)/g; when the addition amount of the sodium polyacrylate is continuously increased, the BET of the nano-modified heavy calcium carbonate is not increased, because the sodium polyacrylate plays a connecting role between the heavy calcium carbonate and the nano calcium carbonate, the addition amount of the sodium polyacrylate can greatly influence the nano-modification effect, the BET of the nano-modified heavy calcium carbonate can be increased along with the increase of the addition amount of the sodium polyacrylate, but the balance can be achieved after a certain amount of sodium polyacrylate is reached, because the surface coating of the heavy calcium carbonate is limited and cannot be increased all the time, the cost can only be increased because the effect after the nano-modification is not increased any more due to the excessive addition of the sodium polyacrylate. The BET is used as a measurement index of nano modification, and the optimal addition amount of the sodium polyacrylate is selected to be 0.8 wt%, so that the problem of the optimal addition amount of the sodium polyacrylate is solved, the production cost can be guided and controlled, and the optimal benefit can be obtained.
(3) The influence of different nano calcium carbonate addition amounts on BET and oil absorption values of nano-modified heavy calcium carbonate is shown in table 3.
TABLE 3
Note: in the table, the oil absorption values of the nano-modified heavy calcium carbonate are all expressed by the results after activation.
From table 3, it can be found that as the addition amount of nano calcium carbonate increases, BET of nano-modified heavy calcium carbonate increases; when the addition amount of the nano calcium carbonate is 20 percent by weight, the BET of the nano modified heavy calcium carbonate can reach 14.48m2G,; when the addition of the nano calcium carbonate is continuously increased, the increase amplitude of the modified heavy calcium carbonate is very small, and the increase of the oil absorption value is larger than that of the previous experiments, so that the modification difficulty in later use is increased, and the cost is increased. Because the nano calcium carbonate is coated on the surface of the heavy calcium carbonate, the addition amount of the nano calcium carbonate can directly influence the effect of nano modified heavy calcium carbonate; with the increase of the nano calcium carbonate, BET and oil absorption values of the nano decorated heavy calcium carbonate are increased, but after a certain amount of nano calcium carbonate is reached, the nano calcium carbonate is completely coated with the heavy calcium carbonate, and then the amount of the nano calcium carbonate is increased, so that the nano calcium carbonate is difficult to coat the surface of the heavy calcium carbonate, a plurality of small nano calcium carbonate particles exist in a system, and at the moment, although the BET is increased to a certain degree, the oil absorption value is increased quickly, so that the cost of raw materials is increased, and the service performance of the nano modified heavy calcium carbonate product is reduced, therefore, the optimal addition amount of the mechanically activated nano modified heavy calcium carbonate is selected as the final addition amount of 20 wt% of the nano calcium carbonate, which is beneficial to guiding and controlling the production cost and obtaining the optimal benefit.
(4) The effect of the addition amount of the ground calcium carbonate modified by different mechanical activation nano-modification on the tensile strength, elongation at break and young's modulus of the polybutylene terephthalate (PBT) resin is shown in table 4.
TABLE 4
Note: in the table, sample 1 is a pure PBT resin added with a ground calcium carbonate sample that is not nano-modified by mechanical activation, and samples 2, 3, and 4 are experimental samples obtained after adding different amounts of the mechanically activated nano-modified ground calcium carbonate prepared in example 4 to the pure PBT resin; the tensile strength, elongation at break and Young's modulus test standards refer to GB/T1040.4-2006.
As can be seen from Table 4: in order to enhance the mechanical property of the PBT resin, the mechanical activation nano-modified heavy calcium carbonate with different addition amounts is selected as a reinforcing filler to reinforce the PBT resin, the compatibility of the heavy calcium carbonate and the PBT resin is further improved as the heavy calcium carbonate is modified to be oleophylic and hydrophobic, but the compatibility of the heavy calcium carbonate and the PBT resin is reduced due to the increase of the particle size of the added particles, a small part of mechanical properties (tensile strength and elongation at break) are reduced, but the mechanical properties (tensile strength and elongation at break) begin to rise back along with the increase of the addition amount of the mechanical activation nano-modified heavy calcium carbonate; meanwhile, the mechanically activated nano-modified heavy calcium carbonate has better binding capacity with PBT resin, when the PBT resin is acted by an external force, the heavy calcium carbonate can absorb a large amount of action energy, and the external force resistance of the filled PBT composite material is enhanced, so that the Young modulus of the filled PBT composite material is improved, the strength of the PBT composite material is enhanced within a certain range, the mechanical property is improved, compared with the non-nano-modified heavy calcium carbonate, the mechanical property of the PBT composite material is greatly improved, the Young modulus is highest under the condition that the optimal addition amount of the mechanically activated nano-modified heavy calcium carbonate is 20 percent and can reach 2.10GPa, the Young modulus is improved by 39.07 percent compared with that of a pure PBT resin added heavy calcium carbonate sample which is not mechanically activated nano-modified, the production and application are favorably guided, and the PBT composite material with the optimal comprehensive performance is obtained.
The protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (10)
1. A preparation method of mechanically activated nano-modified heavy calcium carbonate is characterized by comprising the following steps:
s1, placing a heavy calcium carbonate sample in a forced air drying oven for drying;
s2, adding the dried heavy calcium carbonate sample and sodium polyacrylate into a grinding tank for grinding, and then adding nano calcium carbonate for continuous grinding to obtain a primary product;
and S3, obtaining the mechanically activated nano-modified heavy calcium carbonate by sieving after the reaction is finished.
2. The method for preparing mechanically activated nano-modified heavy calcium carbonate according to claim 1, wherein the drying temperature in step S1 is 90 ℃.
3. The method for preparing mechanically activated nano-modified heavy calcium carbonate according to claim 2, wherein the drying time is 1 hour.
4. The method for preparing mechanically activated nano-modified heavy calcium carbonate according to claim 1, wherein the sample of heavy calcium carbonate in step S2 is 50 g.
5. The method for preparing mechanically activated nano-modified heavy calcium carbonate according to claim 1, wherein the amount of sodium polyacrylate used in step S2 is 0.2-1.0% of the weight of the heavy calcium carbonate sample.
6. The method for preparing mechanically activated nano-modified heavy calcium carbonate according to claim 1, wherein the step S2 comprises adding the dried heavy calcium carbonate sample and sodium polyacrylate into a grinding tank for 10-50 min.
7. The method for preparing mechanically activated nano-modified heavy calcium carbonate according to claim 1, wherein the amount of nano calcium carbonate used in step S2 is 5-25% (wt) of the weight of the heavy calcium carbonate sample.
8. The method for preparing mechanically activated nano-modified heavy calcium carbonate according to claim 1, wherein the grinding time for adding nano calcium carbonate in step S2 is 10-50 min.
9. The method for preparing mechanically activated nano-modified heavy calcium carbonate according to claim 1, wherein the rotation speed during grinding in step S2 is 250-450 r/min.
10. A mechanically activated nano-modified heavy calcium carbonate prepared according to any one of claims 1 to 9, wherein the filler is filled in the polybutylene terephthalate resin in an amount of 10% to 30%.
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