CN110218823A - A kind of high compound X-ray shield material of Z element-natural leather and preparation method thereof - Google Patents
A kind of high compound X-ray shield material of Z element-natural leather and preparation method thereof Download PDFInfo
- Publication number
- CN110218823A CN110218823A CN201910539911.4A CN201910539911A CN110218823A CN 110218823 A CN110218823 A CN 110218823A CN 201910539911 A CN201910539911 A CN 201910539911A CN 110218823 A CN110218823 A CN 110218823A
- Authority
- CN
- China
- Prior art keywords
- composite material
- ray
- preparation
- natural leather
- leather
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C13/00—Manufacture of special kinds or leather, e.g. vellum
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Analysing Materials By The Use Of Radiation (AREA)
Abstract
The preparation method of high Z element-natural leather composite material disclosed by the invention is that the leather of routinely process for tanning production is immersed in the salting liquid containing high Z element, it is combined using active function groups a large amount of in leather with high Z element ion, obtains the high compound X-ray shield material of Z elemental nanoparticles-natural leather.Method preparation process provided by the invention is simply controllable, and material source is abundant, and cheap, reaction condition is mild, does not need special process equipment, is easy to industrial amplification production.The high Z element-natural leather composite density prepared by the method for the invention is small, light weight, is applied in X-ray shield, which has excellent shielding properties, and reduces secondary radiation.In addition, the material had not only solved the disadvantage that conventional polymer shielding material bad mechanical property, but also provide good snugness of fit.
Description
Technical field
The invention belongs to functional material and its preparation technical fields, and in particular to a kind of lightweight, low scattering, high shielding properties
And natural leather base X-ray shield material of high mechanical strength and preparation method thereof.
Background technique
With the development of nuclear physics, ionising radiation is increasingly used in daily life, as medicine is aobvious
Picture, radiotherapy, metal defect detection and material characterization.Meanwhile in nature and industrial production, ionising radiation also can usually be made
There is (Nambiar S, Yeow J T W. Polymer-Composite Materials for for a kind of by-product
Radiation Protection[J]. ACS Applied Materials & Interfaces, 2012, 4(11):
5717-5726.).But if DNA will receive different degrees of destruction, cause when human body is exposed under ionising radiation for a long time
The variation of cell, and then lead to the symptoms such as vomiting, diarrhea, cataract and cancer (Huo Lei, Liu Jianli, Ma Yonghe radiation agent
Amount and protection Beijing [M]: Electronic Industry Press, 2015.), therefore, the ionising radiation of all kinds is all by world health
Tissue international cancer research institution has been classified as a kind of carcinogenic substance (International Agency for Research on
Cancer. IARC Monographs on the Evaluation of Carcinogenic Risks to Humans[M].
Lyon:WHO Press, 2012,100D.).
Ionising radiation refers to that entrained energy is enough that electronics is made to get rid of nuclear constraint, so that atom or molecule be made to send out
Raw ionization radiation (Beijing Wang Jianlong, He Shijun radiation protection basis study course [M]: publishing house, Tsinghua University,
2012.).Ionising radiation according to cause ionization radiation essence can be divided into directly ionizing radiation and indirectly ionizing radiation, wherein
The former mainly includes by He2+The alpha ray of composition and the β ray being made of electronics or positive electron.Range only has alpha ray in air
1 cm can be ignored the harm of human body；Although the aerial range of β ray is big compared with alpha ray, its energy is low, right
The ionization of air is small, easily can be shielded (Chen Wanjin, Chen Yanli, Cai Jie using shield facility or material
Radiation and its Beijing safety protection technique [M]: Chemical Industry Press, 2006.).Indirectly ionizing radiation is mainly penetrated comprising X
Line, gamma-rays and neutron ray, they are all in electroneutral, therefore weaker with directly acting on for substance, but they and substance
Material molecule can be made to ionize and excite when effect, form the active unstable free radical of chemical property, and then make to human body
It is directly related to whether the mankind can safely utilize ionization spoke at serious harm, therefore to effective shielding of indirectly ionizing radiation
It penetrates.
X-ray is the indirectly ionizing radiation being in the most contact in people's daily life, it mainly passes through photoelectric effect, Compton
Scattering and three kinds of modes of Rayleigh scattering are had an effect with substance, are substantially mainly had an effect with the electron outside nucleus of atom
(Nambiar S, Yeow J T W. Polymer-Composite Materials for Radiation Protection
[J] ACS Applied Materials & Interfaces, 2012,4 (11): 5717-5726.).Current theory
Think substance it is directly proportional to the biquadratic of density of material and atomic number to the attenuating of X-ray (Lusic H,
Grinstaff M W. X-ray-Computed Tomography Contrast Agents[J]. Chemical
Reviews, 2013,113 (3): 1641-1666.), therefore, to shield X-ray, mainly using the block of high Z element composition
Body material.
Although block materials have preferable shielding properties to X-ray, it is extremely heavy, is suitable only for being used as stationary applica-tions
Radiation shield, and be not used as the protection of mobile target.Therefore, a large amount of scholars by containing high Z element nano-oxide with
High molecular material is made polymer-based nano-composite materials by different process and is used for X-ray shield (Kim Y, Park
S, Seo Y. Enhanced X-ray Shielding Ability of Polymer–Nonleaded Metal
Composites by Multilayer Structuring[J]. Industrial & Engineering Chemistry
Research, 2015, 54(22): 5968–5973. Chai H, Tang X, Ni M et al. Preparation
and properties of novel, flexible, lead-free X-ray-shielding materials
containing tungsten and bismuth(III) oxide[J]. Journal of Applied Polymer
Science, 2016, 133(10): 43012. Li Q, Wei Q, Zheng W et al. Enhanced Radiation
Shielding with Conformal Light-Weight Nanoparticle–Polymer Composite[J]. ACS
Applied Materials & Interfaces, 2018,10 (41): 35510-35515.).But prepared at present
There are still following problems for polymer-based nano-composite materials: (1) since compatibility poor, synthesis macromolecule and high Z element oxide
The mixing of object nanoparticle is uneven；(2) high Z element oxide nanoparticle used in has fixed crystal form, can be in spy
Determine angle and generate stronger secondary radiation, may cause damages to periphery other staff；(3) machine of the composite material prepared by
Tool intensity is not high, and can decline with the increase of high Z elemental nanoparticles carrying capacity；(4) composite material prepared by lacks hole
Gap structure, permeable gas is poor, and wearable property is insufficient.
Summary of the invention
In response to the problems existing in the prior art, the purpose of the present invention is to provide a kind of loads of the high Z element of lightweight, low scattering
The compound X-ray shield material of natural leather base.
To achieve the above object, The technical solution adopted by the invention is as follows:
Compound X-ray shield material of the invention is the composite material of high Z elemental nanoparticles and natural leather, wherein described
High Z element is at least one of the element of 37≤atomic number≤92, and the natural leather is by ox-hide, sheepskin or pigskin tanning
It forms.Through detecting, the composite material of 1 mm thickness is when shielding the X-ray that average energy is 60 ~ 100 keV, efficiency
Up to 66%.
It is a further object of the present invention to provide the preparation methods of above-mentioned natural leather based composites.To realize above-mentioned mesh
, The technical solution adopted by the invention is as follows:
It is using natural leather as skeleton, using active function groups a large amount of on natural leather in conjunction with high Z element ion, and then obtains
Load the natural leather based composites of high Z elemental nanoparticles.Specifically, comprising the following steps:
(1) high Z element salt is taken to be configured to certain density solution, adjustment solution ph to proper range.
(2) appropriate leather is placed in the solution of above-mentioned configuration, reacts certain time under fixed temperature.
(3) leather is removed from above-mentioned solution, and carries out desolventizing processing.
(4) if necessary, can repeatedly above-mentioned (1)-(3) step to improve high Z element load capacity.
Natural leather used in the above method is raw according to conventional process for tanning by raw material of ox-hide, sheepskin or pigskin
The leather of production.
Used high Z element salt is the soluble-salt of the element comprising atomic number 37 ~ 92.
Used solvent includes but is not limited to the common organic solvents such as water or ethyl alcohol, acetone.
Used concentration of salt solution is 1 ~ 50 wt%, and the mass ratio of salting liquid and leather is 5 ~ 200:1.
Used pH value in reaction is 3 ~ 8.
Used reaction temperature is 10 ~ 60 DEG C.
The used reaction time is 0.5 ~ 24 h.
Used reactive mode includes but is not limited to ultrasonic wave added, shaking table oscillation, overturning oscillation.
Used Desolventizing method includes but is not limited to natural air drying, dehydration of organic solvent, high temperature desolventizing, freezes and do
Dry, decompression desolventizing.
Compared with prior art, the invention has the following advantages:
(1) method provided by the invention is to be supported on high Z element salt in the natural leather with multi-layer fibre structure again
It closes, for this method using amino, the carboxyl, hydroxyl, amide groups isoreactivity group in natural leather, Lai Yugao Z nanoparticle is mutual
Effect, and then is fixed in natural leather, this method it is possible to prevente effectively from nanoparticle reunion.Compared to traditional preparation side
Method, this method can load high Z elemental nanoparticles to more stable and high dispersive.
(2) method provided by the invention is first high Z element salt to be dissolved in solvent appropriate, then solution is impregnated into day
In right leather, finally removes solvent and obtain natural leather based nano composite material.It, can be more since salting liquid is homogeneous system
It is easy and equably penetrates into natural leather, therefore bigger load capacity, the partial size of nanoparticle may be implemented in this method
It is smaller.
(3) present invention is that high Z elemental nanoparticles are carried in natural leather using soluble high Z element salt, therefore
As long as high Z member is known as corresponding soluble-salt, so that it may easily it is supported, therefore this method has extremely strong universality, it is several
It can be adapted for the load of all high Z elements.In addition, high Z element of the invention refers to the element of atomic number Z >=37, phase
For Z >=56 in the prior art, the scope of application is wider, and cost is lower, more universality.
(4) composite material prepared by the present invention can be applied to X-ray shield, since high Z element is by by corresponding salt
Solution is impregnated into natural leather and removes solvent again and loaded, therefore by the condition of control removing solvent, available
Amorphous nanometer of salt grain, thus two can be generated to avoid the shielding material prepared as block shielding material or nano-oxide
The problem of secondary radiation, not only protects target object, but also will not have an impact to ambient enviroment.
(5) composite material prepared by the present invention takes full advantage of the multi-level structure of natural leather, the X in natural leather
Ray occurs repeatedly effect with high Z elemental nanoparticles and X-ray is decayed and absorbed, compared with block materials, the present invention
The composite material of preparation can reach same X-ray shield effect in the case where less dense, and performance is more excellent.This
Outside, the density of the composite material prepared by the present invention is in 1.10 g cm–3Hereinafter, less than the 10% of conventional blocks material, weight
It is lighter, in addition to the radiation shield that can be used as stationary applica-tions, it is also used as the protection of mobile target, application range is wider.
(6) present invention uses the natural leather with natural multi-level structure as basic material, therefore in higher height
Still there is excellent mechanical performance when Z element salt load capacity.The composite material tensile strength of prepared 1.0 mm thickness is up to
25 MPa, tearing strength can reach 70 N mm–1, it is 10 times of polymer-based composite or more.Meanwhile it is prepared by the present invention multiple
The permeable gas of condensation material is 1727 g mm m–2 d–1 kPa–1, it is higher by 100 times of common polymer-based composite or more.
Therefore, composite material prepared by the present invention has good wearable property.
(7) method preparation process provided by the invention is relatively simple, and reaction condition is mild, does not need special processing and sets
It is standby, it is easy to industrial amplification production.
Detailed description of the invention
Fig. 1 is nanometer silver nitrate-sheepskin composite material scanning electron microscope image that embodiment 2 is prepared.
Fig. 2 is nanometer lanthanum nitrate-pigskin composite material scanning electron microscope image that embodiment 6 is prepared.
Fig. 3 is nanometer cesium iodide-ox-hide composite material scanning electron microscope image that embodiment 11 is prepared and first vegetarian noodles
Scan image.
Fig. 4 is nano bismuth molybdate-ox-hide composite material scanning electron microscope image that embodiment 14 is prepared and first vegetarian noodles
Scan image.
Fig. 5 is nanometer sodium tungstate-ox-hide composite material and lead flake X-ray diffractogram that embodiment 9 is prepared.
It is 16 to average energy that Fig. 6, which is the nanometer potassium iodide-sheepskin composite material that is prepared of embodiment 4,33,48,65,
The shielding properties figure of the X-ray of 83 keV.
It is 16 to average energy that Fig. 7, which is the nanometer plumbi nitras-sheepskin composite material that is prepared of embodiment 10,33,48,
65, the shielding properties figure of the X-ray of 83 keV.
It is 16 to average energy that Fig. 8, which is the nanometer lead tungstate-pigskin composite material that is prepared of embodiment 13,33,48,
65, the shielding properties figure of the X-ray of 83 keV.
It is 16 to average energy that Fig. 9, which is the nanometer cesium iodide-ox-hide composite material that is prepared of embodiment 11,33,48,
65, the shielding properties figure of the X-ray of 83 keV.As seen from the figure prepared composite material to the X-ray of different-energy section all
There is stronger shielding properties.
Nanometer bismuth iodide-sheepskin the composite material and 0.1 mm of 1 mm, 2 mm thickness that Figure 10 is prepared for embodiment 12,
Shielding properties figure of the 0.25mm lead flake to the X-ray that average energy is 16,33,48,65,83 keV.
Figure 11 is nanometer barium chloride-ox-hide composite material stress-strain pattern that embodiment 5 is prepared.
Nanometer strontium chloride-ox-hide composite material stress-elongation image that Figure 12 is.
Specific embodiment
Embodiment is given below the present invention is specifically described, it is necessary to which indicated herein to be, the present embodiment is only used
In to further explanation of the invention, it should not be understood as limiting the scope of the invention, for those skilled in the art
The some nonessential improvement and adjustment done according to foregoing invention content, are also considered as and are within the scope of the present invention.With
Number involved in lower embodiment is calculated by quality.
Embodiment 1
Weigh 1 part of SrCl2·6H2O is dissolved in 15 parts of deionized waters, and pH value of solution is adjusted to 3.0 using HCl, takes 1 part of 1.0 mm thick
Chrome tanning ox-hide in the prepared salting liquid, at 20 DEG C using ultrasonic wave added react 0.5 h, then sample is placed in
A nanometer strontium chloride-ox-hide composite material can be obtained in 60 DEG C of oven dryings.
Detection is carried out to obtained composite material and learns that the composite material is 16 keV to average energy, half-value layer is
The shield effectiveness of the X-ray of 0.32 mm Al has reached 95%, is 48 keV to average energy, the X that half-value layer is 0.24 mm Cu
The shield effectiveness of ray has reached 36%.Its tearing strength is detected again, obtains nanometer strontium chloride-pig as shown in figure 12
The stress of veneer composite material-elongation image.Prepared composite material has excellent tearing strength as seen from the figure.
Embodiment 2
Weigh 2 parts of AgNO3198 parts of deionized waters are dissolved in, pH value of solution is adjusted to 4.0 using HCl, take the chromium of 1 part of 0.7 mm thickness
Tan sheepskin overturns 1 h of oscillating reactions at 35 DEG C, sample is then soaked in excessive propanone in the prepared salting liquid
A nanometer silver nitrate-sheepskin composite material can be obtained in middle dehydration.
Detection is carried out to composite material obtained and learns that the composite material is 16 keV to average energy, half-value layer is
The shield effectiveness of the X-ray of 0.32 mm Al has reached 68%, is 48 keV to average energy, the X that half-value layer is 0.24 mm Cu
The shield effectiveness of ray has reached 17%.Electron-microscope scanning is carried out to the material again, obtains nanometer silver nitrate-sheepskin as shown in Figure 1
The scanning electron microscope image of composite material.As seen from the figure, a large amount of silver nitrate nano particles have been loaded on sheepskin fiber, distribution is more
Densification, and the partial size of nanoparticle is smaller.Scanning electron microscope the results show that silver nitrate through the invention the method at
It is supported in sheepskin to function.
Embodiment 3
Weigh 36 parts of SnCl484 parts of acetone are dissolved in, take the chrome tanning pigskin of 1 part of 1.5 mm thickness in the prepared salting liquid,
2 h of shaking table oscillating reactions is used at 10 DEG C, and sample is then placed in a vacuum drying oven drying, a nanometer stannic chloride-can be obtained
Pigskin composite material.
Detection is carried out to obtained composite material and learns that the composite material is 16 keV to average energy, half-value layer is
The shield effectiveness of the X-ray of 0.32 mm Al has reached 73%, is 48 keV to average energy, the X that half-value layer is 0.24 mm Cu
The shield effectiveness of ray has reached 24%.Through detecting, the tearing strength of material is 53 N mm–1, it is seen that prepared composite material
With excellent tearing strength.
Embodiment 4
It weighs 60 parts of KI and is dissolved in 90 parts of deionized waters, pH value of solution is adjusted to 6.0 using NaOH, take the chrome tanning of 1 part of 1.0 mm thickness
Sheepskin reacts 3 h using ultrasonic wave added at 15 DEG C, sample is then placed in shady and cool ventilation in the prepared salting liquid
Locate natural air drying, a nanometer potassium iodide-sheepskin composite material can be obtained.
Obtained composite material is detected, obtains nanometer potassium iodide-sheepskin composite material as shown in FIG. 6 to flat
The shielding properties figure for the X-ray that equal energy is 16,33,48,65,83 keV, prepared composite material is not to as seen from the figure
Co-energy section of X-ray has stronger shielding properties.It is especially 16 keV to average energy, half-value layer is 0.32 mm Al
The shield effectiveness of X-ray reached 96%, the shielding for the X-ray that average energy be 48 keV, half-value layer is 0.24 mm Cu
Efficiency has reached 61%.Through detecting, the permeable gas of material is 1691 g mm m–2 d–1 kPa–1, illustrate prepared composite wood
Material has excellent permeable gas.
Embodiment 5
Weigh 5 parts of BaCl2·6H2O is dissolved in 95 parts of deionized waters, and pH value of solution is adjusted to 5.0 using HCl, takes 1 part of 1.5 mm thick
Chrome tanning ox-hide in the prepared salting liquid, 4 h of shaking table oscillating reactions is used at 60 DEG C, is then freezed sample dry
It is dry, a nanometer barium chloride-ox-hide composite material can be obtained.
Detection is carried out to obtained composite material and learns that the composite material is 16 keV to average energy, half-value layer is
The shield effectiveness of the X-ray of 0.32 mm Al has reached 70%, is 48 keV to average energy, the X that half-value layer is 0.24 mm Cu
The shield effectiveness of ray has reached 31%.Its tensile strength is detected again, obtains nanometer barium chloride-ox as shown in figure 11
Stress-strain pattern of veneer composite material.Prepared composite material has excellent tensile strength as seen from the figure.
Embodiment 6
Weigh 16 parts of La (NO3)3·6H2O is dissolved in 64 parts of ethyl alcohol, takes the chrome tanning pigskin of 1 part of 1.0 mm thickness in the prepared salt
In solution, 12 h of shaking table oscillating reactions is used at 45 DEG C, sample is then placed in a vacuum drying oven drying, can be obtained
Nanometer lanthanum nitrate-pigskin composite material.
Detection is carried out to obtained composite material and learns that the composite material is 16 keV to average energy, half-value layer is
The shield effectiveness of the X-ray of 0.32 mm Al has reached 86%, is 48 keV to average energy, the X that half-value layer is 0.24 mm Cu
The shield effectiveness of ray has reached 35%.Electron-microscope scanning is carried out to the material again, is obtained such as Fig. 2 nanometer lanthanum nitrate-pigskin composite wood
The scanning electron microscope image of material.It can be seen that having loaded a large amount of lanthanum nitrate nanoparticles on pigskin fiber, distribution is more caused
Close, two different sizes are presented in the partial size of nanoparticle, but whole in 100 nm or less.Scanning electron microscope the results show that
The method is successfully supported in pigskin lanthanum nitrate through the invention.
Embodiment 7
Weigh 1.25 parts of Sm (NO3)3·6H2O is dissolved in 58.75 parts of acetone, and the chrome tanning ox-hide of 1 part of 0.5 mm thickness is taken to prepare in this
Salting liquid in, at 30 DEG C overturn 8 h of oscillating reactions, sample is then placed in natural air drying at shady and cool ventilation, can be obtained
Nanometer samaric nitrate-ox-hide composite material.
Detection is carried out to obtained composite material and learns that the composite material is 16 keV to average energy, half-value layer is
The shield effectiveness of the X-ray of 0.32 mm Al has reached 72%, is 48 keV to average energy, the X that half-value layer is 0.24 mm Cu
The shield effectiveness of ray has reached 21%.Through detecting, the permeable gas of material is 1418 g mm m–2 d–1 kPa–1, illustrate made
Standby composite material has excellent permeable gas.
Embodiment 8
Weigh 0.75 part of Gd (NO3)3·5H2O is dissolved in 9.25 parts of ethyl alcohol, takes the chrome tanning pigskin of 1 part of 0.5 mm thickness prepared in this
In salting liquid, 20 h of shaking table oscillating reactions is used at 25 DEG C, then sample is freeze-dried, a nanometer gadolinium nitrate-can be obtained
Pigskin composite material.
Detection is carried out to obtained composite material and learns that the composite material is 16 keV to average energy, half-value layer is
The shield effectiveness of the X-ray of 0.32 mm Al has reached 63%, is 48 keV to average energy, the X that half-value layer is 0.24 mm Cu
The shield effectiveness of ray has reached 24%.Through detecting, the tensile strength of material is 19 MPa, it is seen that prepared composite material tool
There is excellent tensile strength.
Embodiment 9
Weigh 20 parts of Na2WO4·2H2O is dissolved in 20 parts of deionized waters, and pH value of solution is adjusted to 8.0 using HCl, takes 1 part of 0.8 mm
Thick chrome tanning ox-hide overturns 6 h of oscillating reactions at 40 DEG C, was then soaked in sample in the prepared salting liquid
It is dehydrated in amount ethyl alcohol, a nanometer sodium tungstate-ox-hide composite material can be obtained.
Detection is carried out to obtained composite material and learns that the composite material is 16 keV to average energy, half-value layer is
The shield effectiveness of the X-ray of 0.32 mm Al has reached 99%, is 48 keV to average energy, the X that half-value layer is 0.24 mm Cu
The shield effectiveness of ray has reached 42%.X-ray diffraction is carried out to the material and lead flake again, obtains nanometer wolframic acid as shown in Figure 5
Sodium-ox-hide composite material and lead flake X-ray diffractogram.It can be seen that lead flake can generate strong reflection in certain angles,
And prepared composite material without apparent diffraction maximum in the angular range that instrument can be tested, therefore is shown compared to lead flake
Write the generation for reducing secondary radiation.Through detecting, the tensile strength of material is 22 MPa, tearing strength is 69 N mm–1, it is permeable
Gas is 1713 g mm m–2 d–1 kPa–1, illustrate that prepared composite material has excellent mechanical performance and permeable gas.
Embodiment 10
Weigh 0.5 part of Pb (NO3)24.5 parts of deionized waters are dissolved in, pH value of solution is adjusted to 6.0 using NaOH, take 1 part of 0.5 mm
Thick chrome tanning sheepskin uses 24 h of shaking table oscillating reactions at 50 DEG C, then impregnates sample in the prepared salting liquid
It is dehydrated in excess ethyl alcohol, a nanometer plumbi nitras-sheepskin composite material can be obtained.
Obtained composite material is detected, obtains nanometer plumbi nitras-sheepskin composite material as shown in Figure 7 to flat
The shielding properties figure for the X-ray that equal energy is 16,33,48,65,83 keV, prepared composite material is not to as seen from the figure
Co-energy section of X-ray has stronger shielding properties.Detection especially is carried out to obtained composite material and learns that this is compound
The shield effectiveness for the X-ray that material is 16 keV to average energy, half-value layer is 0.32 mm Al has reached 99%, to average energy
Amount is 48 keV, the shield effectiveness for the X-ray that half-value layer is 0.24 mm Cu has reached 48%.Through detecting, the permeable gas of material
For 1618 g mm m–2 d–1 kPa–1, illustrate that prepared composite material has excellent permeable gas.
Embodiment 11
It weighs 1 part of CsI and is dissolved in 199 parts of ethyl alcohol, take the chrome tanning ox-hide of 1 part of 1.0 mm thickness in the prepared salting liquid, 30
24 h of oscillating reactions is overturn at DEG C, and sample is then placed in vacuum oven and sloughs ethyl alcohol, a nanometer cesium iodide-ox-hide can be obtained
Composite material.
Obtained composite material is detected, obtains nanometer cesium iodide-ox-hide composite material as shown in Figure 9 to flat
The shielding properties figure for the X-ray that equal energy is 16,33,48,65,83 keV, prepared composite material is not to as seen from the figure
Co-energy section of X-ray has stronger shielding properties.It is especially 16 keV to average energy, half-value layer is 0.32 mm Al
The shield effectiveness of X-ray reached 99%, the shielding for the X-ray that average energy be 48 keV, half-value layer is 0.24 mm Cu
Efficiency has reached 64%.Electron-microscope scanning and element Surface scan are carried out to the material again, obtained as Fig. 3 nanometer cesium iodide-ox-hide is compound
The scanning electron microscope image and element surface scan figure picture of material.As seen from the figure, the distribution of cesium element and iodine is all and fibre structure
Move towards identical, it was demonstrated that two kinds high Z element has all successfully been supported in ox-hide.
Embodiment 12
Weigh 20 parts of BiI330 parts of deionized waters are dissolved in, HNO is used3PH value of solution is adjusted to 7.0, takes the chromium of 1 part of 0.7 mm thickness
Tan sheepskin uses 4 h of shaking table oscillating reactions in the prepared salting liquid at 60 DEG C, is then removed using freeze-drying
A nanometer bismuth iodide-sheepskin composite material can be obtained in moisture in leather.
1mm thickness is made using splitter in obtained composite material and 2mm is thick, then it is detected respectively again, together
When with lead flake be comparison, obtain 1 mm as shown in Figure 10, nanometer bismuth iodide-sheepskin composite material of 2 mm thickness and 0.1 mm,
Shielding properties figure of the 0.25mm lead flake to the X-ray that average energy is 16,33,48,65,83 keV.It can be seen that 1 mm is thick
Composite material be 16 keV to average energy, the shield effectiveness for the X-ray that half-value layer is 0.32 mm Al has reached 100%,
The shield effectiveness for the X-ray that average energy be 48 keV, half-value layer is 0.24 mm Cu has reached 85%；2 mm are thick to be answered
The shield effectiveness for the X-ray that condensation material is 16 keV to average energy, half-value layer is 0.32 mm Al has reached 100%, to flat
The shield effectiveness for the X-ray that energy is 48 keV, half-value layer is 0.24 mm Cu has reached 94%.The composite material of preparation
There is stronger shielding properties to the X-ray of different-energy section, wherein the X-ray shield performance of the composite material of 1 mm thickness is
It has been more than 0.1 mm lead flake, the X-ray shield performance of the composite material of 2 mm thickness has been over 0.25 mm lead flake.Through detecting,
The tensile strength of material is 20 MPa, tearing strength is 65 N mm–1, permeable gas be 1602 g mm m–2 d–1 kPa–1, say
Bright prepared composite material has excellent mechanical performance and permeable gas.
Embodiment 13
Weigh 2.5 parts of Na2WO4·2H2O is dissolved in 2.5 parts of deionized waters, and pH value of solution is adjusted to 8.0 using NaOH, takes 1 part 1.5
The chrome tanning pigskin of mm thickness reacts 0.5 h using ultrasonic wave added at 10 DEG C, then by sample in the prepared salting liquid
It is placed in excess ethyl alcohol and is dehydrated.
Weigh 10 parts of Pb (NO3)290 parts of deionized waters are dissolved in, HNO is used3PH value of solution is adjusted to 4.0, it will be in upper step
Sample is placed in the prepared salting liquid, and 12 h of oscillating reactions is overturn at 40 DEG C, sample is then placed in 60 DEG C of baking ovens
A nanometer lead tungstate-pigskin composite material can be obtained in middle drying.
Obtained composite material is detected, obtains nanometer lead tungstate-pigskin composite material as shown in Figure 8 to flat
The shielding properties figure for the X-ray that equal energy is 16,33,48,65,83 keV, prepared composite material is not to as seen from the figure
Co-energy section of X-ray has stronger shielding properties.Detection especially is carried out to obtained composite material and learns that this is compound
The shield effectiveness for the X-ray that material is 16 keV to average energy, half-value layer is 0.32 mm Al has reached 99%, to average energy
Amount is 48 keV, the shield effectiveness for the X-ray that half-value layer is 0.24 mm Cu has reached 58%.Through detecting, the permeable gas of material
For 1727 g mm m–2 d–1 kPa–1, illustrate that prepared composite material has excellent permeable gas.
Embodiment 14
Weigh 7.5 parts of Bi (NO3)3And 142.5 parts of deionized waters are added, use HNO3PH value of solution is adjusted to 3.0, takes 1 part 1.5
The chrome tanning ox-hide of mm thickness uses 1 h of shaking table oscillating reactions at 20 DEG C, then sets sample in the prepared salting liquid
Make its natural air drying in shady place.
Weigh 6 parts of Na2MoO4·2H2O is dissolved in 24 parts of deionized waters, and pH value of solution is adjusted to 8.0 using NaOH, by upper step
In sample be placed in the prepared salting liquid, at 30 DEG C using ultrasonic wave added soak 2 h, then sample was placed in
It is dehydrated in amount acetone, nano bismuth molybdate-ox-hide composite material can be obtained.
Electron-microscope scanning and element Surface scan are carried out to the material, obtain nano bismuth molybdate as shown in Figure 4-ox-hide composite wood
The scanning electron microscope image and element surface scan figure picture of material.As seen from the figure, the distribution of bismuth element and molybdenum element is all walked with fibre structure
To identical, it was demonstrated that two kinds high Z element has all successfully loaded in the leather.Again obtained composite material detect
To know, the shield effectiveness for the X-ray which is 16 keV to average energy, half-value layer is 0.32 mm Al has reached 99%,
The shield effectiveness for the X-ray that average energy be 48 keV, half-value layer is 0.24 mm Cu has reached 72%.Through detecting, material
Tensile strength is 22 MPa, tearing strength is 55 N mm–1, permeable gas be 1680 g mm m–2 d–1 kPa–1, it is seen that it is made
Standby composite material has excellent mechanical strength and permeable gas.
Claims (10)
1. a kind of high compound X-ray shield material of Z element-natural leather, which is characterized in that be high Z elemental nanoparticles and day
The composite material of right leather, the composite material of 1 mm thickness when being shielded to average energy for the X-ray of 60 ~ 100 keV,
Efficiency is up to 66%.
2. compound X-ray shield material according to claim 1, which is characterized in that the high Z element is 37≤atomic number
At least one of the element of number≤92.
3. compound X-ray shield material according to claim 1 or 2, which is characterized in that the natural leather by ox-hide,
Sheepskin or pigskin tanning form.
4. a kind of preparation of the high compound X-ray shield material of Z element-natural leather as claimed in any one of claims 1-3
Method, which is characterized in that the preparation method includes: to react in the salting liquid for be placed in natural leather high Z element, has been reacted
At rear taking-up leather and carry out desolventizing processing；Above-mentioned steps are repeated 0 ~ 5 time to get compound X-ray shield material.
5. the preparation method according to claim 4, which is characterized in that the solvent in the salting liquid of the high Z element is water
Or organic solvent, the organic solvent are ethyl alcohol or acetone；The method of the desolventizing processing is natural air drying, organic solvent is de-
Water, high temperature desolventizing, freeze-drying or decompression desolventizing.
6. preparation method according to claim 4 or 5, which is characterized in that the concentration of the salting liquid of the high Z element be 1 ~
50 wt%, pH value are 3 ~ 8.
7. preparation method according to claim 6, which is characterized in that the salting liquid and natural leather of the high Z element press 5
The mass ratio of ~ 200:1 is reacted.
8. preparation method according to claim 7, which is characterized in that the reaction is carried out under the conditions of 10 ~ 60 DEG C
's.
9. preparation method according to claim 7 or 8, which is characterized in that when a length of 0.5 ~ 24 h of each reaction.
10. preparation method according to claim 9, which is characterized in that in the reaction process, can also use ultrasound, shake
Bed oscillation or overturning oscillation are to accelerate reaction speed.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910539911.4A CN110218823B (en) | 2019-06-21 | 2019-06-21 | high-Z element-natural leather composite X-ray shielding material and preparation method thereof |
| PCT/CN2019/098976 WO2020252861A1 (en) | 2019-06-21 | 2019-08-02 | High-z-element-natural leather composite x-ray shielding material and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910539911.4A CN110218823B (en) | 2019-06-21 | 2019-06-21 | high-Z element-natural leather composite X-ray shielding material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110218823A true CN110218823A (en) | 2019-09-10 |
| CN110218823B CN110218823B (en) | 2021-07-23 |
Family
ID=67814069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910539911.4A Active CN110218823B (en) | 2019-06-21 | 2019-06-21 | high-Z element-natural leather composite X-ray shielding material and preparation method thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN110218823B (en) |
| WO (1) | WO2020252861A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113650362A (en) * | 2021-08-11 | 2021-11-16 | 四川大学 | Preparation method of X-ray protection material based on superfine fiber membrane |
| CN115232893A (en) * | 2022-08-18 | 2022-10-25 | 四川大学 | Flexible neutron shielding material based on collagen fibers and preparation method |
| CN115410736A (en) * | 2022-10-11 | 2022-11-29 | 四川大学 | Ray shielding material based on core-shell structure nano particles and preparation method thereof |
| CN115410736B (en) * | 2022-10-11 | 2024-05-28 | 四川大学 | Ray shielding material based on core-shell structure nano particles and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624508A (en) * | 2009-07-28 | 2010-01-13 | 四川大学 | Method for preparing radar absorbing materials with hide glue fibril |
| CN105040163A (en) * | 2015-08-19 | 2015-11-11 | 四川大学 | Method for manufacturing radar wave absorption material with collagen fibers as template |
| CN105219895A (en) * | 2015-10-27 | 2016-01-06 | 四川大学 | A kind of leather with capability of electromagnetic shielding and preparation method thereof |
| CN106714537A (en) * | 2016-12-29 | 2017-05-24 | 四川大学 | Broadband electromagnetic wave shielding material and preparation method thereof |
| CN109022638A (en) * | 2018-06-11 | 2018-12-18 | 四川大学 | The low reflection of one kind, high-selenium corn electromagnetic shielding material and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU500735A1 (en) * | 1974-06-12 | 1977-03-05 | Means to protect leather materials from ionizing radiation | |
| JP2001242288A (en) * | 2000-02-29 | 2001-09-07 | Toshiba Corp | Radiation shielding material, and radiation shielding suit, radiation shield and radiation shielding equipment using it |
| CN108997732A (en) * | 2018-09-06 | 2018-12-14 | 含山县金中环装饰材料有限公司 | A kind of preparation method of permanent protective property rtificial leather |
| CN109461511B (en) * | 2018-10-24 | 2020-03-20 | 上海都浩医用新材料有限公司 | X-ray protective cloth and X-ray protective clothing |
| CN109887630B (en) * | 2019-04-15 | 2024-05-07 | 广州新莱福磁材有限公司 | Magnetic super-soft X/gamma ray protection film material with decoration or direct printing and preparation method thereof |
-
2019
- 2019-06-21 CN CN201910539911.4A patent/CN110218823B/en active Active
- 2019-08-02 WO PCT/CN2019/098976 patent/WO2020252861A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624508A (en) * | 2009-07-28 | 2010-01-13 | 四川大学 | Method for preparing radar absorbing materials with hide glue fibril |
| CN105040163A (en) * | 2015-08-19 | 2015-11-11 | 四川大学 | Method for manufacturing radar wave absorption material with collagen fibers as template |
| CN105219895A (en) * | 2015-10-27 | 2016-01-06 | 四川大学 | A kind of leather with capability of electromagnetic shielding and preparation method thereof |
| CN106714537A (en) * | 2016-12-29 | 2017-05-24 | 四川大学 | Broadband electromagnetic wave shielding material and preparation method thereof |
| CN109022638A (en) * | 2018-06-11 | 2018-12-18 | 四川大学 | The low reflection of one kind, high-selenium corn electromagnetic shielding material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113650362A (en) * | 2021-08-11 | 2021-11-16 | 四川大学 | Preparation method of X-ray protection material based on superfine fiber membrane |
| CN115232893A (en) * | 2022-08-18 | 2022-10-25 | 四川大学 | Flexible neutron shielding material based on collagen fibers and preparation method |
| CN115410736A (en) * | 2022-10-11 | 2022-11-29 | 四川大学 | Ray shielding material based on core-shell structure nano particles and preparation method thereof |
| CN115410736B (en) * | 2022-10-11 | 2024-05-28 | 四川大学 | Ray shielding material based on core-shell structure nano particles and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110218823B (en) | 2021-07-23 |
| WO2020252861A1 (en) | 2020-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Pottathara et al. | UV-Induced reduction of graphene oxide in cellulose nanofibril composites | |
| Kuruba et al. | Guar gum: Structural and electrochemical characterization of natural polymer based binder for silicon–carbon composite rechargeable Li-ion battery anodes | |
| CN110218823A (en) | A kind of high compound X-ray shield material of Z element-natural leather and preparation method thereof | |
| Zou et al. | Preparation and functional study of cellulose/carbon quantum dot composites | |
| Peng et al. | PCN-224/rGO nanocomposite based photoelectrochemical sensor with intrinsic recognition ability for efficient p-arsanilic acid detection | |
| Ma et al. | Non-enzymatic electrochemical hydrogen peroxide sensing using a nanocomposite prepared from silver nanoparticles and copper (II)-porphyrin derived metal-organic framework nanosheets | |
| Ramesh et al. | Electrochemical and spectroscopic characterization of quinone functionalized exfoliated graphite | |
| Milošević et al. | In situ generation of Ag nanoparticles on polyester fabrics by photoreduction using TiO 2 nanoparticles | |
| Carvalho et al. | Removal of metal ions from aqueous solution by chelating polymeric hydrogel | |
| Zhang et al. | Impact of leach on lead vanado-iodoapatite [Pb5 (VO4) 3I]: An infrared and Raman spectroscopic study | |
| He et al. | Fluorescent hydrogels based on oxidized carboxymethyl cellulose with excellent adsorption and sensing abilities for Ag+ | |
| Krishnapandi et al. | Surface etched carbon nanofiber companied ytterbium oxide for pinch level detection of fungicides carbendazim | |
| Hur et al. | A study on fabrication of polypyrrole@ lignin composite and electrical sensing and metal ion adsorption capabilities | |
| Pothan et al. | XPS studies of chemically modified banana fibers | |
| Menazea et al. | Gamma radiation introduces improvement in Ac conductivity behavior and dielectric characterization of CuONPs@ PVP-PVA nano matrix films prepared by one-potential laser ablation method | |
| Grishchenko et al. | Electromagnetic interference shielding of carbon fibers oxidatively brominated in the liquid-phase | |
| Dong et al. | A Coordination Strategy for TixSn1–xO2 Solid Solution Nanocubes Wrapped by Reduced Graphene Oxide as a Candidate for Lithium‐Ion‐Battery Anodes | |
| Latham et al. | Cation-oxygen geometry in polymer electrolytes: interpretation of EXAFS results | |
| CN110197734B (en) | Preparation method of X-ray shielding material based on natural leather | |
| CN115410736B (en) | Ray shielding material based on core-shell structure nano particles and preparation method thereof | |
| US20170229725A1 (en) | Phytic acid based metallogel and applications thereof | |
| Ren et al. | Electrochemical sensor based on molecularly imprinted polymer and graphene oxide nanocomposite for monitoring glyphosate content in corn | |
| CN113650362B (en) | Preparation method of X-ray protection material based on superfine fiber membrane | |
| Mufida et al. | The Effect of Addition Fe3O4 on the rGO/Fe3O4 Composite on Glucose Biosensor Performance | |
| Jia et al. | Biosynthesis of gold nanoparticles using novel bamboo (Bambusa chungii) leaf extracts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |