CN101805238A - Preparation method of high-strength spherical agglomerated boron particles - Google Patents
Preparation method of high-strength spherical agglomerated boron particles Download PDFInfo
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- CN101805238A CN101805238A CN 201010131010 CN201010131010A CN101805238A CN 101805238 A CN101805238 A CN 101805238A CN 201010131010 CN201010131010 CN 201010131010 CN 201010131010 A CN201010131010 A CN 201010131010A CN 101805238 A CN101805238 A CN 101805238A
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Abstract
The invention discloses a preparation method of high-strength spherical agglomerated boron particles, which comprises the following steps: (1) dissolving 8-9 weight parts of polyurethane prepolymer adhesive into 15-25 times of ethyl acetate or ethanol to be uniformly mixed with 0.5-1.2 weight parts of isocyanate curing agents to obtain premix; (2) adding 80-95 weight parts of amorphous boron powder into the premix to be mixed; (3) adding 0.02-0.05 weight part of curing catalyst; and (4) screening the obtained particle materials with a standard screen of 60-140 meshes, and carrying out vacuum drying. The boron particles prepared by the method of the invention have higher strength and can not be broken easily when being added into propellants, and the obtained agglomerated boron particles have controllable particle size and higher granulating rate.
Description
Technical field
The present invention relates to a kind of preparation method of high-strength spherical agglomerated boron particles, refer more particularly to the preparation method of fuel-rich propellant with agglomerated boron particles.
Background technology
The boron powder has advantages such as quality calorific value and volume calorific value height, density are big, is the preferred fuels of solid rocket ramjet with fuel-rich propellant.Because the H that the amorphous boron powder surface is contained
3BO
3Deng acidic impurities, the hydroxyl generation condensation reaction with hydroxy-terminated polybutadienes (HTPB) tamanori prepolymer sharply increases the viscosity of Composite Propellant Slurry, to such an extent as to can't cast.In addition, other impurity in the amorphous boron powder such as magnesium powder, MgCl
2, MgO, MgB
2, B
2O
3Deng, the easy moisture absorption that has is easy to make boron particles surface adsorption large quantity of moisture, causes the boron powder incompatible with the propelling agent binder system, thus must amorphous boron powder be handled, to improve boracic fuel-rich propellant processing performance and combustionproperty.
Processing to amorphous boron powder both at home and abroad comprises that mainly the surface coats and two kinds of methods of agglomeration granulation.Though the surface coats technology and the combustionproperty that can to a certain degree improve propelling agent, the granularity of surperficial Boron Coated powder is less, and specific surface area is big, and the add-on of boron powder still is difficult to improve in the propelling agent, to such an extent as to very limited to the raising of firing speed and burning rate pressure exponent; From satisfying the engineering application demand, it is an effective way that the boron powder is reunited.United States Patent (USP) 3646174 was once reported a kind of technology of amorphous boron powder agglomeration granulation; this method can be prepared granular boron powder; but use a large amount of hydrochloric ethers to make solvent and directly be thrown in the air; can't reclaim; and gained boron powder degree is bigger, and the primary combustion ejection efficiency is low, secondary combustion is difficult to igniting and abundant problem such as burning and big particle diameter boron powder exists.
Summary of the invention
It is simple to the purpose of this invention is to provide a kind of technological process, and the preparation method of the spherical agglomerated boron particles that balling ratio height and granule strength are higher is to overcome the deficiencies in the prior art.
Implementation procedure of the present invention is as follows:
A kind of preparation method of high-strength spherical agglomerated boron particles may further comprise the steps:
(1) 8～9 weight part polyurethane prepolymer tamanoris are dissolved in 15～25 times the ethyl acetate or ethanol, with 0.5～1.2 weight part isocyanates solidifying agent mix Preblend (the control temperature of charge is 30 ± 5 ℃);
(2) 80～90 weight part amorphous boron powders are added in the above-mentioned Preblend mix;
(3) add the curing catalysts of 0.02～0.05 weight part again;
(4) the gained granular material is crossed 60 orders～140 mesh standard sieves, vacuum-drying.
Described polyurethane prepolymer tamanori is hydroxy-terminated polybutadienes (HTPB), carboxy terminated polybutadiene (CTPB) or polyvinyl butyral acetal.
Described isocyanates solidifying agent is 1,4-tolylene diisocyanate (TDI), isoflurane chalcone diisocyanate (IPDI) or hexamethylene diisocyanate (HDI).
Described curing catalysts is dibutyl tin dilaurate (T-12), in the use T-12 is dissolved in 10～20 times the ethyl acetate.
For improving the combustionproperty of boron particles, also added the ammoniumper chlorate of 3～7 weight parts in the above-mentioned steps (1).
Amorphous boron powder passes through modification before use, remove surface impurity, concrete grammar is as follows: 2～5 weight part surface-modifying agents are dissolved in 100～200 times the acetone or alcohol, the amorphous boron powder that adds 95～98 weight parts is at 50 ℃ of stirring reaction 24h, except that after desolvating, dry 72h under 70 ℃ obtains surface modification boron powder.Described surface-modifying agent is TriMethylolPropane(TMP) (TMP) or trolamine (TEA), the most handy acetone solution of TMP, the most handy dissolve with ethanol of TEA.
In above-mentioned steps (1), (2) and (3), being blended in the planetary vertical kneader of material carried out.
In the above-mentioned steps (4), gained spherical agglomerated boron particles shape material is crossed 60 orders～80 orders and 100 orders～140 mesh standard sieves respectively.
Advantage of the present invention and positively effect:
(1) boron particles for preparing of the inventive method has higher intensity, add to be difficult in the propelling agent broken.
(2) the kneader stirring rake of Cai Yonging pre-mixed regiment in whipping process by processes such as shearing, extruding, can increase the density of agglomerated boron particles.
(3) the agglomerated boron particles particle diameter for preparing of the inventive method is controlled, and balling ratio is higher.
Embodiment
Used amorphous boron powder, HTPB, CTPB, TDI, IPDI, HDI, T-12, ethyl acetate and the acetone etc. of the present invention are market and buy.
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1
In planetary vertical kneader, with 8.5g polyurethane prepolymer tamanori hydroxy-terminated polybutadienes (HTPB, E
OH=7.8 * 10
-4Mol/g) use the 170ml acetic acid ethyl dissolution, add 0.6g 1,4-tolylene diisocyanate solidifying agent (TDI) premix is (the control temperature of charge is 30 ± 5 ℃) evenly, then 85g boron powder is added thorough mixing in the above-mentioned premix material, at last 0.03g dibutyl tin dilaurate (T-12) is dissolved in the 0.5g ethyl acetate, adds to thorough mixing in the said mixture material; The gained granular material is crossed 60 orders～80 orders and 100 orders～140 mesh standard sieves respectively, at 50 ℃ of following vacuum-drying 72h.
Performance test
1, granule strength test
Testing tool is a ZQJ-II intelligence granule strength trier.
Testing method: agglomerated boron particles is sieved processing by the standard sub-sieve, by the size classification, in order to make experiment have stronger operability and stability, get the spherical agglomerated boron particles that an amount of particle diameter is 1.8mm～2.1mm, (0～500N) measures particulate ultimate compression strength (on the particle diameter direction suffered power), divides three groups of random sampling, and every group of test is 5 under identical condition by ZQJ-II intelligence granule strength trier, calculate its mean value, the results are shown in Table 1.
The granule strength of table 1 reunion boron powder
As can be seen from Table 1, adopt the spherical agglomerated boron particles of this method preparation to have higher intensity, be added in the planetary vertical kneader difficult broken.
2, B/HTPB suspension rheology testing
Testing tool is the RS-300 rheometer.
Testing method: boron powder (amorphous boron powder or agglomerated boron particles) and HTPB tamanori are made uniform suspension by the quality proportioning at 2: 3, and test b/HTPB suspension liquid rheological property behind 50 ℃ of insulation 30min is 10s with the shearing rate
-1The time mixture apparent viscosity and yield value represent that test result sees Table 2.
The rheological property of table 2B/HTPB suspension
Can find out that by table 2 result the suspension that agglomerated boron particles and HTPB form has lower yield value and apparent viscosity than amorphous boron powder, substantially not in time increase and increase.
3, packing density of particle test
Testing tool is the 25mL graduated cylinder, analytical balance.
Testing method: 1. get the 25mL graduated cylinder, take by weighing graduated cylinder quality m
0G; 2. in graduated cylinder, add a kind of agglomerated boron particles of particle size range, take by weighing the total mass m of graduated cylinder and agglomerated boron particles
1G.At this moment, the pine of this particle size range agglomerated boron particles dress tap density is 40 (m
1-m
0) kg/m
3The graduated cylinder that 3. will fill agglomerated boron particles carries out jolt ramming, and the graduated cylinder bottom is apart from the about 1cm of desktop when vibrating at every turn.In process of the test, after the agglomerated boron particles of each particle size range vibration 50 times, the volume V mL of record agglomerated boron particles, at this moment, the jolt ramming tap density of this particle size range agglomerated boron particles is 1000 (m
1-m
0)/V kg/m
3, until the basic no change of pellet density; 4. get 1 graduated cylinder in addition and carry out weighing, repeat 2., 3. step is measured 3 times the tap density of each particle size range agglomerated boron particles, averages, and test result sees Table 3.
The tap density of table 3 amorphous boron powder and reunion boron powder relatively
By table 3 result as can be seen, the spherical agglomerated boron particles of preparation has bigger pine dress tap density and jolt ramming tap density than amorphous boron powder, can further improve the density of boracic fuel-rich propellant thus.
4, the application of high-strength spherical agglomerated boron particles in boron powder fuel-rich propellant of the present invention's preparation
The agglomerated boron particles that obtains has carried out the specimen preparation of fuel-rich propellant prescription, and concrete prescription consists of: HTPB binder system 26%, and boron powder (amorphous boron powder or agglomerated boron particles) 35%, AP 34%, Mg/Al alloy 5%.Sample preparation methods through mediating, is tested the apparent viscosity in this Composite Propellant Slurry 6h according to conventional compositepropellent method for making sample, the results are shown in Table 4.
The apparent viscosity of table 4 boracic fuel-rich propellant medicine slurry over time
Under identical preparation propelling agent condition, amorphous boron powder becomes glutinous at kneading beginning process Chinese medicine slurry, and crosslinking reaction takes place, and obvious " gel " phenomenon that occurs can't be prepared the boracic fuel-rich propellant.Result in the table 4 shows, increase in time, the apparent viscosity of boracic fuel-rich propellant medicine slurry increases, and the application of agglomerated boron particles in propelling agent significantly reduces the apparent viscosity of Composite Propellant Slurry, can solve the consistency difficult problem of boron powder and binder system preferably, and processing performance can satisfy the casting requirement.
Embodiment 2
2g surface-modifying agent TMP is dissolved in the acetone of 200ml, adds the 98g amorphous boron powder at 50 ℃ of stirring reaction 24h, and 70 ℃ of following vacuum-dryings remove desolvates, and obtains surface modification boron powder.In planetary vertical kneader, with 8.5g polyurethane prepolymer tamanori hydroxy-terminated polybutadienes (HTPB, hydroxyl value: 7.8 * 10
-4Mol/g) use the 170ml acetic acid ethyl dissolution, add ammoniumper chlorate 5g and 0.6g 1,4-tolylene diisocyanate solidifying agent (TDI) premix is even, and the control temperature of charge is 30 ± 5 ℃; 85g surface modification boron powder is added thorough mixing in the above-mentioned premix material; (T-12) is dissolved in the 0.5g ethyl acetate with the 0.03g dibutyl tin dilaurate, adds to thorough mixing in the said mixture material; The gained granular material is crossed 60 orders～80 orders and 100 orders～140 mesh standard sieves, at 50 ℃ of following vacuum-drying 72h.
Performance test
Testing tool and testing method the results are shown in following table 5 and table 6 with embodiment 1.
The granule strength of table 5 reunion boron powder
The rheological property of table 6 boron powder density result and B/HTPB suspension
Embodiment 3
This routine implementation method is substantially the same manner as Example 2, and different is that the tamanori prepolymer adopts carboxy terminated polybutadiene, and consumption is 9.0g, and solidifying agent adopts HDI, and consumption is 1.05g, and the ammoniumper chlorate consumption is 7.0g.
Performance test
Testing tool and testing method the results are shown in following table 7 and table 8 with embodiment 1.
The granule strength of table 7 reunion boron powder
The rheological property of table 8 boron powder density result and B/HTPB suspension
Embodiment 4
This routine implementation method is substantially the same manner as Example 2, and different is surface-modifying agent trolamine (TEA), and consumption is 2g, and the tamanori prepolymer adopts hydroxy-terminated polybutadienes (HTPB, hydroxyl value: 6.8 * 10
-4Mol/g), consumption is 9.0g, and solidifying agent adopts IPDI, and consumption is 0.80g.
Performance test
Testing tool and testing method the results are shown in following table 9 and table 10 with embodiment 1.
The granule strength of table 9 reunion boron powder
The rheological property of table 10 boron powder density result and B/HTPB suspension
Claims (9)
1. the preparation method of a high-strength spherical agglomerated boron particles may further comprise the steps:
(1) 8～9 weight part polyurethane prepolymer tamanoris are dissolved in 15～25 times the ethyl acetate or ethanol, with 0.5～1.2 weight part isocyanates solidifying agent mix Preblend;
(2) 80～95 weight part amorphous boron powders are added in the above-mentioned Preblend mix;
(3) add the curing catalysts of 0.02～0.05 weight part again;
(4) the gained granular material is crossed 60 orders～140 mesh standard sieves, vacuum-drying.
2. the preparation method of high-strength spherical agglomerated boron particles according to claim 1, it is characterized in that: described polyurethane prepolymer tamanori is hydroxy-terminated polybutadienes, carboxy terminated polybutadiene or polyvinyl butyral acetal.
3. the preparation method of high-strength spherical agglomerated boron particles according to claim 1, it is characterized in that: described isocyanates solidifying agent is 1,4-tolylene diisocyanate, isoflurane chalcone diisocyanate or hexamethylene diisocyanate.
4. the preparation method of high-strength spherical agglomerated boron particles according to claim 1, it is characterized in that: described curing catalysts is a dibutyl tin dilaurate, during use dibutyl tin dilaurate is dissolved in 10～20 times the ethyl acetate.
5. the preparation method of high-strength spherical agglomerated boron particles according to claim 1 is characterized in that: also added the ammoniumper chlorate of 3～7 weight parts in the step (1), to improve the combustionproperty of boron particles.
6. according to the preparation method of one of any described high-strength spherical agglomerated boron particles of claim 1 to 5, it is characterized in that: described amorphous boron powder uses preceding through modification, method is as follows: 2～5 weight part surface-modifying agents are dissolved in 100～200 times the acetone or alcohol, the amorphous boron powder reaction back that adds 95～98 weight parts is except that desolvating, and drying obtains surface modification boron powder.
7. the preparation method of high-strength spherical agglomerated boron particles according to claim 6, it is characterized in that: described surface-modifying agent is TriMethylolPropane(TMP) or trolamine.
8. according to the preparation method of one of any described high-strength spherical agglomerated boron particles of claim 1 to 5, it is characterized in that: in step (1), (2) and (3), being blended in the planetary vertical kneader of material carried out.
9. according to the preparation method of one of any described high-strength spherical agglomerated boron particles of claim 1 to 5, it is characterized in that: in the step (4), gained spherical agglomerated boron particles shape material is crossed 60 orders～80 orders and 100 orders～140 mesh standard sieves respectively.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989362A (en) * | 2012-12-20 | 2013-03-27 | 西安近代化学研究所 | Efficient granulation method of amorphous boron powder |
| CN103396856A (en) * | 2013-07-05 | 2013-11-20 | 西安近代化学研究所 | Boron-magnesium composite particle for fuel-rich propellant |
| CN104030866A (en) * | 2014-06-06 | 2014-09-10 | 中国航天科工集团第六研究院四十六所 | Seismic charge prepared by waste hydroxyl-terminated polyb (HTPB) solid propellant slurry and application thereof |
| CN105148796A (en) * | 2015-09-07 | 2015-12-16 | 中国兵器科学研究院宁波分院 | Spray granulation method of active nano aluminum powder |
| CN106854124A (en) * | 2015-12-08 | 2017-06-16 | 上海新力动力设备研究所 | A kind of boron-based fuel-rich processing method of boron powder |
| CN108299136A (en) * | 2018-03-13 | 2018-07-20 | 中国人民解放军国防科技大学 | Surface treatment method of amorphous boron powder and amorphous boron powder for propellant |
| CN108892597A (en) * | 2018-07-24 | 2018-11-27 | 西安近代化学研究所 | A kind of method of agglomeration of boron magnesium composite powder |
| CN115108873A (en) * | 2022-06-08 | 2022-09-27 | 西安兰科工控技术有限责任公司 | High-activity nano aluminum powder granulation method |
Citations (1)
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| CN101531556A (en) * | 2009-04-24 | 2009-09-16 | 西安近代化学研究所 | Method for granulating amorphous boron powder |
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2010
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Patent Citations (1)
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| CN101531556A (en) * | 2009-04-24 | 2009-09-16 | 西安近代化学研究所 | Method for granulating amorphous boron powder |
Non-Patent Citations (1)
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989362A (en) * | 2012-12-20 | 2013-03-27 | 西安近代化学研究所 | Efficient granulation method of amorphous boron powder |
| CN103396856A (en) * | 2013-07-05 | 2013-11-20 | 西安近代化学研究所 | Boron-magnesium composite particle for fuel-rich propellant |
| CN104030866A (en) * | 2014-06-06 | 2014-09-10 | 中国航天科工集团第六研究院四十六所 | Seismic charge prepared by waste hydroxyl-terminated polyb (HTPB) solid propellant slurry and application thereof |
| CN104030866B (en) * | 2014-06-06 | 2017-04-19 | 中国航天科工集团第六研究院四十六所 | Seismic charge prepared by waste hydroxyl-terminated polyb (HTPB) solid propellant slurry and application thereof |
| CN105148796A (en) * | 2015-09-07 | 2015-12-16 | 中国兵器科学研究院宁波分院 | Spray granulation method of active nano aluminum powder |
| CN105148796B (en) * | 2015-09-07 | 2017-07-28 | 中国兵器科学研究院宁波分院 | A kind of Spray granulation method of active nano aluminium powder |
| CN106854124A (en) * | 2015-12-08 | 2017-06-16 | 上海新力动力设备研究所 | A kind of boron-based fuel-rich processing method of boron powder |
| CN108299136A (en) * | 2018-03-13 | 2018-07-20 | 中国人民解放军国防科技大学 | Surface treatment method of amorphous boron powder and amorphous boron powder for propellant |
| CN108299136B (en) * | 2018-03-13 | 2020-05-19 | 中国人民解放军国防科技大学 | Surface treatment method of amorphous boron powder and amorphous boron powder for propellant |
| CN108892597A (en) * | 2018-07-24 | 2018-11-27 | 西安近代化学研究所 | A kind of method of agglomeration of boron magnesium composite powder |
| CN115108873A (en) * | 2022-06-08 | 2022-09-27 | 西安兰科工控技术有限责任公司 | High-activity nano aluminum powder granulation method |
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Application publication date: 20100818 |