CN101624508B - Method for preparing radar absorbing materials with hide glue fibril - Google Patents
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- CN101624508B CN101624508B CN200910060136A CN200910060136A CN101624508B CN 101624508 B CN101624508 B CN 101624508B CN 200910060136 A CN200910060136 A CN 200910060136A CN 200910060136 A CN200910060136 A CN 200910060136A CN 101624508 B CN101624508 B CN 101624508B
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Abstract
The invention discloses a method for preparing radar absorbing materials with hide glue fibril, comprising the following steps: the hide glue fibril is absolutely dried into 100 parts, and 100 parts of the hide glue fibril and 1000-2000 parts of dispersing agents are added in a reaction device, the pH is adjusted to 7.5-10.0, and then 80-300 parts of aldehydes compound are added in the device, the mixture is stirred and reacted for 2-8 hours at the 30-60 DEG C, and then 68-110 parts of metal salt are added, and the mixture is stirred and reacted for 2-6 hours at the 30-60 DEG C, and is dried. The radar absorbing materials prepared by the hide glue fibril has wide frequency band and strong adsorption capacity to radar waves, and the source of the raw material is wide, the price is low, the density is low, the quality is light, the processability is good, and the material can be filmed directly, thereby well solving the problems that the wave-absorbing material can lose the wave adsorption efficiency in the formation of the application and in the disposition and using process when being used as coating material.
Description
Technical field
The invention belongs to the preparing technical field of radar absorbing, be specifically related to a kind of method with preparing radar absorbing materials with hide glue fibril.
Background technology
Radar absorbing both can be used for the stealthy of aircraft, guided missile, naval vessels, vehicle etc.; The wall material that also can be used for microwave unreflected chamber; To alleviate interference, improve the accuracy of measuring, also can be used as the antiradiation material of electronic products such as radiation-resistant clothes, utensil and mobile phone, computer, TV etc.
Usually, radar absorbing can be divided into inorganic absorbing material and organic absorbing material two big classes.The mineral-type radar absorbing has iron system (like polycrystalline iron fiber, iron carbonyl), carbon system (like graphite, thomel) and pottery system (like silit) absorbing material.Organic type of material obsorbing radar waves is generally the high molecular polymer of conduction, as polypyrrole, polyaniline, Schiff's base and salt thereof etc. (Li Wanzhi is etc. camouflage coating technology [M] for Hu Chuanqi, Wang Zhihui. Beijing: Chemical Industry Press, 2005.01:69-90).Though inorganic radar absorbing has good absorbing property, and it inhales ripple bandwidth, reflection loss (RL) height, and its density is big, and the area density of the camouflage coating of processing is often greater than 5kg/m
2, thereby its application receives certain restriction.In recent years, but because organic polymer conductivity type absorbing material light weight, the good big area film forming of flexibility, thereby its research obtained fast-developing (Xie Junlei, Du Shiguo, Shi Dongmei. New Type Radar absorbing material progress [J] .2008,07:58-61; Mu Zhongguo, Zhu Jinhua, Wang Yuansheng, etc. the present Research of radar absorbing and development prospect [J]. colloid and polymerization, 2002,20 (4): 40-43; Wang Y M.Research progress on radar absorbingmaterials [J] .Military Microwave, 2008, Supplement:36-47).
In organic polymer conductivity type absorbing material, Schiff's base (Schiff base) and salt thereof (Schiff base salt) are very important one type of material obsorbing radar waves.Schiff's base belongs to the structural conductive absorbing material, and it is by aldehyde compound (CHO) and primary amine (NH
2) under weak basic condition, react and one type of imine derivative of generation, the Schiff alkali salt is Schiff's base and some metals ions such as Fe
3+, Al
3+, Ag
+, Cu
2+Deng, react and a kind of complex compound of generating (Yu Jiugao is etc. the preparation [J] of macromole retinyl Schiff's base salt microwave absorption for Wang Shaomin, Gao Jianping. aerospace material technology, 2002,2:41-43; Ghasemi, Hossienpour A, Morisako A, et al.Investigation of themicrowave absorptive behavior of doped barium ferrites [J] .Mater Design, 2008,29:112-117).Because the metals ion of introducing in the Schiff alkali salt provides and has received electronic orbit; The conductivity and the electromagnetic performance of complex compound change to some extent; Absorption band to radar wave is widened, receptivity strengthen (Ding Chunxia, Fan Congbin, Zhang Luohan. synthetic and the The study of radar absorbing property [J] of novel retinene1 Schiff alkali salt. chemical industry and engineering; 2006,27 (04): 4-6; Li Y, Liu R, Zhang Z, et al.Synthesis and characterization of nanocrystallineBaFe
9.6Co
0.8Ti
0.8M
0.8O
19Particles [J] .Mater Chem Phys, 2000,64:256-259).Like retinyl Schiff's base salt (the retinyl Schiffbase salt) reflection loss stronger to having of radar wave by people such as Wang Shoutai development; Thickness is at 2.0 millimeters retinyl Schiff's base salt; Can reach-10dB in of the reflection loss (RL) of some range of frequency, and its density is merely 1.1g/cm radar wave
3(Wang Shoutai, woods insults, Huang Bin, etc. the research of retinyl Schiff's base absorbing material [J]. aerospace material technology .1989,4:21-27; Fan Congbin, Xiong Guoxuan. the progress of microwave Absorbent of electric schiff bases [J]. New Chemical Materials, 2005,33 (02): 60-62; Zhang Yanru, Wang Zhiyong. the application prospect [J] of Schiff's base in stealth material. material engineering, 2008 (supplementary issue): 366-369; Leniec G, Kaczmarek S M, Typek J, et al.Magnetic andspectroscopic properties of gadolinium tripodal Schiff base complex [J] .Solid State Sci, 2007,9:267-273; Courric S, Tran V H.The electromagnetic of blends of poly (p-phenylene-vinylene) derivatives [J] .Polymers for Advanced Technologies, 2000,11 (6): 273-279; Li W G, Wan M X.Electrical and magnetic properties of conjugated Schiff basepolymers [J] .J Appl Polym Sci, 1996,62:941-950).
Though Schiff's base and salt absorbing material thereof have absorbing property preferably, also be in conceptual phase at present, do not obtain using comparatively widely.Its major cause is because the character of Schiff's base and salt thereof is very unstable, and addition reaction takes place for Yi Yushui, hydrogen halide, hydrosulphite and prussic acid etc., makes its altered chemical structure and loses certain suction ripple effect, therefore is not suitable as coating and uses.In addition, prices such as the used quadrol of Schiff's base and salt thereof, aniline, phenylenediamine are also relatively more expensive owing to preparing, thereby limited its widespread use.
Summary of the invention
The objective of the invention is the problem that exists to prior art, provide isolated materials with hide glue fibril in a kind of skin or solid leather wastes with livestock animals to prepare the method for radar absorbing.This method not only makes prepared radar absorbing cheap, and has also avoided Schiff's base and salt thereof must use the problem of being brought with the coating mode as radar absorbing.This has not only developed new radar absorbing, and transforms the new field of having opened up for the high value of materials with hide glue fibril.
For reaching the object of the invention the method with preparing radar absorbing materials with hide glue fibril is provided; This method is earlier 100 parts of materials with hide glue fibril over dry meters and dispersion agent to be added in the reaction unit for 1000～2000 parts, and regulates pH to 7.5～10.0, adds 80～300 parts of aldehyde compounds then; In 30～60 ℃ of following stirring reactions of temperature 2～8 hours; Add 68～110 parts of metal-salts again, continue at 30～60 ℃ of following stirring reactions of temperature 2～6 hours, at last 30～60 ℃ of following vacuum-dryings of temperature 12～18 hours; Can obtain to have the materials with hide glue fibril material of radar-wave absorbing characteristic, more than the umber of used material be weight part.
In the aforesaid method used materials with hide glue fibril be the livestock animals skin by conventional process hides pretreatment technology remove the materials with hide glue fibril that is chopped into 0.2～2.0 millimeter of median size behind the interfibrillar substance, tannery not the animal skin leftover bits of tanning remove by conventional process hides pretreatment technology and be chopped into the materials with hide glue fibril of 0.2～2.0 millimeter of median size or in the commodity materials with hide glue fibril any behind the interfibrillar substance.In order to reduce cost; Preferred wherein livestock animals skin by conventional process hides pretreatment technology remove the materials with hide glue fibril that is chopped into 0.2～2.0 millimeter of median size behind the interfibrillar substance or tannery not the animal skin leftover bits of tanning remove the materials with hide glue fibril that is chopped into 0.2～2.0 millimeter of median size behind the interfibrillar substance by conventional process hides pretreatment technology, more preferably tannery not the animal skin leftover bits of tanning remove the materials with hide glue fibril that is chopped into 0.2～2.0 millimeter of median size behind the interfibrillar substance by conventional process hides pretreatment technology.
Used dispersion agent is any in absolute ethyl alcohol, methyl alcohol or the acetone in the aforesaid method.Preferred absolute ethyl alcohol.
Used aldehyde compound is any in LUTARALDEHYDE, salicylic aldehyde, Alpha-Methyl phenylbutyraldehyde, phenylacetic aldehyde, phenylpropyl aldehyde or the retinene1 in the aforesaid method.Preferred LUTARALDEHYDE, salicylic aldehyde, phenylpropyl aldehyde or retinene1.
Used metal-salt is any in iron trichloride, aluminum chloride, Silver Nitrate, ferric sulfate, copper sulfate, dichloride barium, dichloride copper or the Nickel Chloride in the aforesaid method, preferred iron trichloride, aluminum chloride, Silver Nitrate, dichloride barium, dichloride copper or Nickel Chloride.
The ethanolic soln of alkaline matters such as the pH available hydrogen sodium oxide of reaction system, Pottasium Hydroxide is regulated in the aforesaid method.
The base material that the present invention selects for use---materials with hide glue fibril is a kind of structural protein, mainly comes from the skin of livestock animals (pig, ox, sheep), is one of renewable animal organism matter of stock number maximum in the world.Because constituting the tropocollagen molecule of collegen filament is the triple helix structures that are made up of three polypeptied chains; Every the spiral peptide chain approximately contains 1052 amino acid; And amino acid whose put in order have strict-(Gly-X-Y-)-periodically (and Zhang Ting has. tanning chemistry [M]; Chengdu: press of Sichuan University, 2003,10:25-26; Friess W.Collagen-biomaterial for drug delivery [J] .Eur JPharm Biopharm; 1998; 45:113-136), not only store the electricdipole and the molecule bound charge of higher density in addition in the tropocollagen molecule, demonstrating tangible electret state; Have performances such as static, polarization, and also there is the amino (NH of some amount in the tropocollagen molecule side chain
2), thereby adopt the inventive method, and under weak basic condition, itself and aldehyde compound are reacted, make the amino (NH on the collegen filament
3) change into imines (C=N) structure promptly generates the structure of similar amino-acid schiff base, and further generates the similar amino-acid schiff base salt with conduction infinitesimal with reacting metal salt, thus the radar-wave absorbing performance of having given materials with hide glue fibril.In addition; Because collegen filament intramolecularly and the intermolecular water molecules that passes through are with hydrogen bonded; Therefore collegen filament also contain >=moisture of 12.0% (wt%) usually; And because the specific heat of water capacity is big, temperature can obviously not rise behind the collegen filament absorbing radar wave, and its infrared emittance can obviously not raise yet.
Because with collagen or the fiber condition after the inventive method processing; And the physics between the collegen filament twines, interleaving effect; And the chemically crosslinked between hydroxyl, carboxyl, amino in the tropocollagen molecule; Thereby the method that not only can adopt similar papermaking is shaped and directly processes film (thin layer) shape, also can pressure forming, directly process thickness and be 0.5～5.0 millimeter film; And the collegen filament film that is obtained has certain mechanical strength; Thereby solved the shaping problem of absorbing material in application (traditional absorbing material when using, be to be mixed with material such as sizing agent to be coated with feed liquid, brushing forms microwave absorbing coating at body surface after drying) preferably and as can the certain problem of inhaling the ripple effect of forfeiture in coating configuration, the use.
Certainly do not get rid of yet the inventive method is handled materials with hide glue fibril radar absorbing and other chemical substances that the back obtains; Process coating shape mixture together like sizing agent etc., brushing forms 0.5～5.0 mm thick on the surface of corresponding equipment, wall coating plays the effect of absorbing radar wave.Nonetheless; Because of the physics between the collegen filament twines, interleaving effect; And the chemically crosslinked effect between hydroxyl, carboxyl, amino in the tropocollagen molecule, it receives the influence of water, hydrogen halide, hydrosulphite and prussic acid also little than the Schiff alkali salt that prior art obtained.
The present invention also has following advantage:
(1) different with traditional preparation process Schiff alkali salt absorbing material, reaction of the present invention is carried out in organic medium, thereby helps the stable generation of Schiff alkali salt, prevents the decomposition of Schiff alkali salt, makes material obtain stronger absorbing property.
(2) the inventive method can be through selecting different aldehyde compounds and metal-salt for use, and the consumption that changes reactant, makes materials with hide glue fibril obtain wave-sucking performance in various degree.
(3) materials with hide glue fibril after the inventive method chemically modified is to the absorption of radar wave, except that have inhale the ripple bandwidth (inhale wave frequency scope 1～18GHz), receptivity strong (reflection loss can reach-24dB) characteristics, also have the low (＜0.9g/cm of density
3) (testing method: the film that cuts 10 * 10cm; Claim its weight; Adopt GB/T451.3-1989 " assay method of paper and cal(l)iper " to measure thickness, use weight then, be the density of material divided by area and thickness), light weight, good, the easy film forming characteristics of processibility.
(4) the used materials with hide glue fibril raw material sources of the present invention are extensive, products obtained therefrom cheap.
(5) the inventive method technology is simple, ripe, easy handling control.
Description of drawings
Fig. 1 is the suction wave reflection loss design sketch of 2 millimeters of the embodiment of the invention 1 gained materials with hide glue fibril radar absorbing thickness; Fig. 2 is the suction wave reflection loss design sketch of 1.5 millimeters of the embodiment of the invention 1 gained materials with hide glue fibril radar absorbing thickness; Fig. 3 is the suction wave reflection loss design sketch of the embodiment of the invention 2 gained materials with hide glue fibril radar absorbings; Fig. 4 is the suction wave reflection loss design sketch of the embodiment of the invention 3 gained materials with hide glue fibril radar absorbings; Fig. 5 is the suction wave reflection loss design sketch of the embodiment of the invention 6 gained materials with hide glue fibril radar absorbings; Fig. 6 is the suction wave reflection loss design sketch of the embodiment of the invention 9 gained materials with hide glue fibril radar absorbings.
Embodiment
Through embodiment the present invention is carried out concrete description below; Be necessary to be pointed out that at this following examples only are used for the present invention is described further; Can not be interpreted as restriction to protection domain of the present invention; The person skilled in the art in this field makes some nonessential improvement and adjustment according to the content of the invention described above, still belongs to protection scope of the present invention.
In addition, worth explanation is that the weight of the materials with hide glue fibril that following examples are used all is in over dry.
Carry out fragmentation, washing after ox-hide removed unhairing and non-collagen tissue,,, obtain particle diameter and be 0.2～2.0 millimeter materials with hide glue fibril then 40 ℃ of following vacuum-dryings 12 hours with the NaAc-Hac buffered soln processing of pH 4.2 6 hours.
With the materials with hide glue fibril that obtains 50 grams and absolute ethyl alcohol 800 grams, add and have in the reaction kettle of whisking appliance, TM and reflux condensing tube adjusting pH to 8.0; Add salicylic aldehyde 50 grams then; Heat up in 50 ℃ of following stirring reactions 6 hours, add iron trichloride 55 grams again, continue at 50 ℃ of following stirring reactions 3 hours; At last with reactant 50 ℃ of following vacuum-dryings 14 hours, promptly get salicylic aldehyde and Fe (III) and modify cattle-hide collagen fibers Fe-Sa-CF radar absorbing.
The pigskin leather leftover eluriated carry out fragmentation, washing after clean,,, obtain particle diameter and be 0.2～2.0 millimeter materials with hide glue fibril then 40 ℃ of following vacuum-dryings 12 hours with the NaAc-Hac buffered soln processing of pH 4.2 6 hours.
With the materials with hide glue fibril that obtains 50 grams and absolute ethyl alcohol 800 grams, add and have in the reaction kettle of whisking appliance, TM and reflux condensing tube adjusting pH to 10.0; Add salicylic aldehyde 50 grams then; Heat up in 60 ℃ of following stirring reactions 2 hours, add Silver Nitrate 34 grams again, continue at 60 ℃ of following stirring reactions 2 hours; At last with reactant 60 ℃ of following vacuum-dryings 12 hours, promptly get salicylic aldehyde and Ag (I) and modify pigskin collagen fiber Ag-Sa-CF radar absorbing.
Carry out fragmentation, washing after pigskin removed unhairing and non-collagen tissue,,, obtain particle diameter and be 0.2～2.0 millimeter materials with hide glue fibril then 40 ℃ of following vacuum-dryings 12 hours with the NaAc-Hac buffered soln processing of pH 4.2 6 hours.
With the materials with hide glue fibril that obtains 50 grams and absolute ethyl alcohol 900 grams, add and have in the reaction kettle of whisking appliance, TM and reflux condensing tube adjusting pH to 9.0; Add LUTARALDEHYDE 40 grams then; Heat up in 40 ℃ of following stirring reactions 8 hours, add iron trichloride 55 grams again, continue at 40 ℃ of following stirring reactions 5 hours; At last with reactant 40 ℃ of following vacuum-dryings 16 hours, promptly get LUTARALDEHYDE and Fe (III) and modify pigskin collagen fiber Fe-Gl-CF radar absorbing.
The sheepskin leather leftover eluriated carry out fragmentation, washing after clean,,, obtain particle diameter and be 0.2～2.0 millimeter materials with hide glue fibril then 40 ℃ of following vacuum-dryings 12 hours with the NaAc-Hac buffered soln processing of pH 4.2 6 hours.
With the materials with hide glue fibril that obtains 50 grams and methyl alcohol 650 grams, add and have in the reaction kettle of whisking appliance, TM and reflux condensing tube adjusting pH to 8.0; Add Alpha-Methyl phenylbutyraldehyde 65 grams then; Heat up in 45 ℃ of following stirring reactions 7 hours, add ferric sulfate 40 grams again, continue at 45 ℃ of following stirring reactions 3 hours; At last with reactant 45 ℃ of following vacuum-dryings 16 hours, promptly get Alpha-Methyl phenylbutyraldehyde and Fe (III) and modify sheepskin collegen filament Fe-Be-CF radar absorbing.
Carry out fragmentation, washing after sheepskin removed unhairing and non-collagen tissue,,, obtain particle diameter and be 0.2～2.0 millimeter materials with hide glue fibril then 40 ℃ of following vacuum-dryings 12 hours with the NaAc-Hac buffered soln processing of pH 4.2 6 hours.
With the materials with hide glue fibril that obtains 50 grams and absolute ethyl alcohol 800 grams, add and have in the reaction kettle of whisking appliance, TM and reflux condensing tube adjusting pH to 7.5; Add phenylpropyl aldehyde 56 grams then; Heat up in 40 ℃ of following stirring reactions 8 hours, add dichloride copper 34 grams again, continue at 40 ℃ of following stirring reactions 4 hours; At last with reactant 40 ℃ of following vacuum-dryings 16 hours, promptly get phenylpropyl aldehyde and Cu (II) and modify sheepskin collegen filament Cu-Php-CF radar absorbing.
The pigskin leather leftover eluriated carry out fragmentation, washing after clean,,, obtain particle diameter and be 0.2～2.0 millimeter materials with hide glue fibril then 40 ℃ of following vacuum-dryings 12 hours with the NaAc-Hac buffered soln processing of pH 4.2 6 hours.
With the materials with hide glue fibril that obtains 50 grams and absolute ethyl alcohol 700 grams, add and have in the reaction kettle of whisking appliance, TM and reflux condensing tube adjusting pH to 8.0; Add phenylpropyl aldehyde 56 grams then; Heat up in 50 ℃ of following stirring reactions 6 hours, add iron trichloride 55 grams again, continue at 50 ℃ of following stirring reactions 4 hours; At last with reactant 50 ℃ of following vacuum-dryings 14 hours, promptly get phenylpropyl aldehyde and Fe (III) and modify pigskin collagen fiber Fe-Php-CF radar absorbing.
The not tanning sheepskin leftover bits that tannery's sheet tannage is obtained carry out fragmentation, washing, then 40 ℃ of following vacuum-dryings 12 hours, obtain particle diameter and be 0.2～2.0 millimeter materials with hide glue fibril.
With the materials with hide glue fibril that obtains 10 grams and absolute ethyl alcohol 120 grams, add and have in the reaction kettle of whisking appliance, TM and reflux condensing tube adjusting pH to 9.0; Add retinene1 30 grams then; Heat up in 50 ℃ of following stirring reactions 8 hours, add dichloride barium 9 grams again, continue at 50 ℃ of following stirring reactions 6 hours; At last with reactant 50 ℃ of following vacuum-dryings 14 hours, promptly get retinene1 and Ba (II) and modify sheepskin collegen filament Ba-Re-CF radar absorbing.
The not tanning pigskin leftover bits that tannery's sheet tannage is obtained carry out fragmentation, washing, then 40 ℃ of following vacuum-dryings 12 hours, obtain particle diameter and be 0.2～2.0 millimeter materials with hide glue fibril.
With the materials with hide glue fibril that obtains 50 grams and acetone 750 grams, add and have in the reaction kettle of whisking appliance, TM and reflux condensing tube adjusting pH to 9.5; Add phenylacetic aldehyde 48 grams then; Heat up in 55 ℃ of following stirring reactions 4 hours, add copper sulfate 50 grams again, continue at 55 ℃ of following stirring reactions 3 hours; At last with reactant 55 ℃ of following vacuum-dryings 13 hours, promptly get phenylacetic aldehyde and Cu (II) and modify pigskin collagen fiber Cu-Pha-CF radar absorbing.
Embodiment 9
The ox-hide leather leftover eluriated carry out fragmentation, washing after clean,,, obtain particle diameter and be 0.2～2.0 millimeter materials with hide glue fibril then 40 ℃ of following vacuum-dryings 12 hours with the NaAc-Hac buffered soln processing of pH 4.2 6 hours.
With the materials with hide glue fibril that obtains 50 grams and absolute ethyl alcohol 1000 grams, add and have in the reaction kettle of whisking appliance, TM and reflux condensing tube adjusting pH to 8.5; Add salicylic aldehyde 50 grams then; Heat up in 30 ℃ of following stirring reactions 8 hours, add Nickel Chloride 47 grams again, continue at 30 ℃ of following stirring reactions 6 hours; At last with reactant 30 ℃ of following vacuum-dryings 18 hours, promptly get salicylic aldehyde and Ni (II) and modify cattle-hide collagen fibers Ni-Sa-CF radar absorbing.
The not tanning ox-hide leftover bits that tannery's sheet tannage is obtained carry out fragmentation, washing, then 40 ℃ of following vacuum-dryings 12 hours, obtain particle diameter and be 0.2～2.0 millimeter materials with hide glue fibril.
With the materials with hide glue fibril that obtains 50 grams and absolute ethyl alcohol 800 grams, add and have in the reaction kettle of whisking appliance, TM and reflux condensing tube adjusting pH to 8.0; Add LUTARALDEHYDE 40 grams then; Heat up in 30 ℃ of following stirring reactions 8 hours, add aluminum chloride 48 grams again, continue at 30 ℃ of following stirring reactions 6 hours; At last with reactant 30 ℃ of following vacuum-dryings 18 hours, promptly get LUTARALDEHYDE and Al (III) and modify cattle-hide collagen fibers Al-Gl-CF radar absorbing.
With market pig materials with hide glue fibril 10 grams and absolute ethyl alcohol 100 grams, add and have in the reaction kettle of whisking appliance, TM and reflux condensing tube adjusting pH to 8.0; Add retinene1 30 grams then; Heat up in 50 ℃ of following stirring reactions 8 hours, add Silver Nitrate 7 grams again, continue at 50 ℃ of following stirring reactions 6 hours; At last with reactant 50 ℃ of following vacuum-dryings 14 hours, promptly get retinene1 and Ag (I) and modify pigskin collagen fiber Ag-Re-CF radar absorbing.
Application examples 1
Take by weighing Fe-Sa-CF 75 grams by embodiment 1 preparation; Extrusion molding under 0.4MPa pressure is processed 200 * 200 millimeters, and thickness is 2.0 millimeters film; Adopt RCS (RCS) method to measure its radar-wave absorbing characteristic in 1～18GHz scope, reflection loss is as shown in Figure 1.Visible from scheming, Fe-Sa-CF in 10～18GHz scope, to the reflection loss (RL) of radar wave all-more than the 10dB.
Application examples 2
Take by weighing Fe-Sa-CF 50 grams by embodiment 1 preparation, extrusion molding under 0.4MPa pressure is processed 200 * 200 millimeters, and thickness is 1.5 millimeters film, adopts the RCS method to measure its radar-wave absorbing characteristic in 1～18GHz scope, and reflection loss is as shown in Figure 2.Visible from scheming, Fe-Sa-CF has certain absorption to radar wave in 1～18GHz scope, particularly in 8～18GHz scope, reflection loss (RL) also-more than the 10dB.
Application examples 3
Take by weighing Ag-Sa-CF 50 grams by embodiment 2 preparations, extrusion molding under 0.4MPa pressure is processed 200 * 200 millimeters, and thickness is 1.5 millimeters film, adopts the RCS method to measure its radar-wave absorbing characteristic in 1～18GHz scope, and reflection loss is as shown in Figure 3.Visible from scheming, Ag-Sa-CF has stronger absorption to radar wave, and the maximum reflection loss can reach-24dB.
Application examples 4
Take by weighing Fe-Gl-CF 50 grams by embodiment 3 preparations, extrusion molding under 0.4MPa pressure is processed 200 * 200 millimeters, and thickness is 1.5 millimeters film, adopts the RCS method to measure its radar-wave absorbing characteristic in 1～18GHz scope, and reflection loss is as shown in Figure 4.Visible from scheming, Fe-Gl-CF has certain absorption to radar wave, and the maximum reflection loss is-10.83dB.
Application examples 5
Take by weighing Fe-Php-CF 50 grams by embodiment 6 preparations, extrusion molding under 0.4MPa pressure is processed 200 * 200 millimeters, and thickness is 1.5 millimeters film, adopts the RCS method to measure its radar-wave absorbing characteristic in 1～18GHz scope, and reflection loss is as shown in Figure 5.Visible from scheming, Fe-Php-CF has certain absorption to radar wave, but not as application examples 1, application examples 2 and application examples 3.If film thickness increases, its frequency band of inhaling ripple can further be widened, absorption intensity further improves.
Application examples 6
Take by weighing Ni-Sa-CF 50 grams by embodiment 9 preparations, extrusion molding under 0.4MPa pressure is processed 200 * 200 millimeters, and thickness is 1.5 millimeters film, adopts the RCS method to measure its radar-wave absorbing characteristic in 1～18GHz scope, and reflection loss is as shown in Figure 6.Visible from scheming, Ni-Sa-CF has certain absorption to radar wave, but not as application examples 1, application examples 2 and application examples 3.If film thickness increases, its frequency band of inhaling ripple can further be widened, absorption intensity further improves.
Claims (3)
1. method with preparing radar absorbing materials with hide glue fibril; This method is earlier 100 parts of materials with hide glue fibril over dry meters and dispersion agent to be added in the reaction unit for 1000～2000 parts, and regulates pH to 7.5～10.0, adds 80～300 parts of aldehyde compounds then; In 30～60 ℃ of following stirring reactions of temperature 2～8 hours; Add 68～110 parts of metal-salts again, continue at 30～60 ℃ of following stirring reactions of temperature 2～6 hours, at last 30～60 ℃ of following vacuum-dryings of temperature 12～18 hours; Can obtain to have the materials with hide glue fibril material of radar-wave absorbing characteristic
Wherein used materials with hide glue fibril be the livestock animals skin by conventional process hides pretreatment technology remove the materials with hide glue fibril that is chopped into 0.2～2.0 millimeter of median size behind the interfibrillar substance, tannery not the animal skin leftover bits of tanning remove by conventional process hides pretreatment technology and be chopped into the materials with hide glue fibril of 0.2～2.0 millimeter of median size or in the commodity materials with hide glue fibril any behind the interfibrillar substance; The pH of reaction system regulates with the ethanolic soln of sodium hydroxide, Pottasium Hydroxide alkalescence material; Used dispersion agent is any in absolute ethyl alcohol, methyl alcohol or the acetone; Used aldehyde compound is any in LUTARALDEHYDE, salicylic aldehyde, phenylpropyl aldehyde, Alpha-Methyl phenylbutyraldehyde, phenylacetic aldehyde or the retinene1; Used metal-salt is any in iron trichloride, ferric sulfate, aluminum chloride, Silver Nitrate, dichloride barium, dichloride copper, copper sulfate or the Nickel Chloride of solubility,
More than the umber of used material be weight part.
2. the method with preparing radar absorbing materials with hide glue fibril according to claim 1, used aldehyde compound is any in LUTARALDEHYDE, salicylic aldehyde, phenylpropyl aldehyde or the retinene1 in this method.
3. the method with preparing radar absorbing materials with hide glue fibril according to claim 1 and 2, used metal-salt is any in iron trichloride, aluminum chloride, Silver Nitrate, dichloride barium, dichloride copper or the Nickel Chloride of solubility in this method.
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| CN105040163B (en) * | 2015-08-19 | 2017-08-08 | 四川大学 | The method that material obsorbing radar waves are prepared by template of collagenous fibres |
| CN108929629A (en) * | 2018-07-30 | 2018-12-04 | 四川大学 | A kind of preparation method of phase transformation Infrared stealthy materials |
| CN110218823B (en) * | 2019-06-21 | 2021-07-23 | 四川大学 | high-Z element-natural leather composite X-ray shielding material and preparation method thereof |
| RU2728735C1 (en) * | 2019-11-15 | 2020-07-30 | федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский ядерный университет "МИФИ" (НИЯУ МИФИ) | Method of producing radar absorbent material |
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| CN1868587A (en) * | 2006-06-27 | 2006-11-29 | 四川大学 | Collagenous fibers carried iron catalyst, prepn. method and use thereof |
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