CN109692652A - A kind of normal-temperature nano composite getter - Google Patents
A kind of normal-temperature nano composite getter Download PDFInfo
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- CN109692652A CN109692652A CN201910127454.8A CN201910127454A CN109692652A CN 109692652 A CN109692652 A CN 109692652A CN 201910127454 A CN201910127454 A CN 201910127454A CN 109692652 A CN109692652 A CN 109692652A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/2805—Sorbents inside a permeable or porous casing, e.g. inside a container, bag or membrane
Abstract
The present invention relates to the normal-temperature nano composite getters for vacuum heat-insulating plate, mixture comprising alkaline earth oxide, transition metal oxide and rare-earth oxide, the alkaline earth oxide is calcium oxide, transition metal oxide is the mixture of at least one of palladium oxide, titanium dioxide and copper, cobalt, nickel metal oxide, and rare-earth oxide is cerium oxide；The normal-temperature nano composite getter be three kinds of oxides homogeneous mixture in the form of a powder sealed package in ventilated polymeric bag.Getter of the invention is not necessarily to activated at, and easy to use, price is low, has excellent performance, at normal temperature can residual gas in efficient absorption vacuum heat-insulating plate, maintain good vacuum environment in plate, prolong the service life.
Description
Technical field
The invention belongs to vaccum thermal insulation technique fields, and in particular to a kind of normal-temperature nano composite getter.
Background technique
With the continuous development of global industry process, on the one hand a large amount of consumption of fossil energy face energy crisis, separately
One side problem of environmental pollution is also on the rise, and energy-saving and emission-reduction have become whole world focus of attention.Vacuum heat-insulating plate (Vacuum
Insulation Panel, abbreviation VIP) as a kind of novel super insulating material, thermal coefficient is down to 0.002-
0.004W/mK is the 1/10 of Conventional insulation thermal coefficient, and thickness is only the 1/7-1/10 of Conventional insulation, to reach
It, extensively should be in refrigerator, frozen products insulated container etc. to the higher field of thermal requirements and new to heat preservation energy-saving, section space-efficient purpose
The exterior-wall heat insulation of type energy saving building.The vacuum spacer of VIP is sealed using plastic hot melt, generally using temperature no more than 150 DEG C,
And initial gas pressure is successively according to residual air capacity and the size influenced on thermal coefficient in 0.1Pa~100Pa inside VIP
H2O, H2, CO, CO2, O2And N2Deng.The Insulating mechanism of VIP is that gas molecule mean free path (has with pressure under vacuum conditions
Close) it is greater than pore character size (related with aperture), the gas heat transfer in hole is suppressed, and hole is smaller, to vacuum degree
It is required that lower.Since glass fiber core material hole is larger (10~100 μm), when pressure is more than that 10Pa gas heat away begins
Existing, when pressure is more than 1KPa, thermal coefficient is more than 0.012W/mK, loses superinsulation performance, VIP failure.
In order to solve these problems, many scholars have done a lot of research work:
Patent CN1046581C discloses a kind of equipment and its manufacturing method that vacuum is maintained in insulating jacket, the equipment
It opens wide and including a top being preferably container made of the gas impermeable material of aluminium；The first lamination is placed in the bottom of container
Piece is placed with the second laminate on the top of container the first laminate to be completely covered.First laminate is by barium-lithium alloy
It is made, and the second laminate is made by a kind of powder of desiccant material, the powder of desiccant material also selectively contains one
Kind metal oxide containing precious metals and a kind of material powder for preventing desiccant from squeezing.The getter equipment in addition to complex process, price
Except valuableness, barium-lithium alloy meets water and releases big calorimetric and hydrogen, there is burning and risk of explosion, and in addition barium metal nocuousness human body is strong
Health, it is unfriendly to environment.
Patent CN200986085Y discloses a kind of getter device of vacuum heat-insulating plate and is added to vacuum heat-insulating plate
In structure, which includes the getter in container and container, and getter is by desiccant, barium-lithium alloy, cobalt oxide
The powder of equal substances mixes；Container is flake, grid aperture less than the rice paper packaging bag of getter particle size, is used
When the getter is laid in VIP core material plate, the getter contact area is big, and inspiratory effects are good.But this getter
There is safe and environment-friendly, the problem of being detrimental to health brought by barium, in addition, being adsorbed in the getter device exposure air
Gas be difficult to extract during being encapsulated into VIP, and there are one longer deflation course after VIP sealing, in VIP
Portion's vacuum degree has very big negative effect.
Patent CN104066502B discloses a kind of getter device containing getter material combination, the getter material
Mixture of the material comprising Metal Palladium, cerium oxide and copper oxide, for removing the H in vacuum2And CO, what Metal Palladium itself had had
Hydrogen-absorbing ability, but palladium absorption hydrogen is reversible, and can be released at 50 DEG C or more, this is for being possible to apply at 50 DEG C or more
The VIP of environment is unfavorable.In addition, the mixture mixes removal H with desiccant material2O, the H in VIP2O is most important residual
Residual air body needs to remove using efficient adsorbent material, otherwise H2O can be such that the mixture of Metal Palladium, cerium oxide and copper oxide inhales
Attached H2It declines to a great extent with the performance of CO, which does not propose specific requirement to desiccant.
Patent CN106732326A discloses a kind of gettering material and preparation method and getter, the gettering material are
Cerium oxide and copper oxide are subjected to semi-reduction, obtain the mixture of metal simple-substance and metal oxide, then is mixed with adsorption enhancer
Conjunction obtains the gettering material, and metallic cerium simple substance chemical activity is high, inflammable in air, there is some potential safety problems.In addition, should
Getter is to residual gas H most important in VIP2The adsorption effect of O is poor.
In addition to this, traditional getter requires to use in 400 DEG C or more activation, and is less than suitable for pressure
In the vacuum environment of 0.01Pa, total inspiratory capacity is small.It is hidden in the presence of safety with getter therefore, it is necessary to solve VIP in the prior art
Suffer from, not environmentally, be detrimental to health and the problems such as pumping property cannot be met the requirements；Meanwhile it needing for remaining in VIP plate
The condition etc. that gas flow, gaseous species and VIP cannot be heated at high temperature, develops dedicated getter.
Summary of the invention
The purpose of the present invention is to provide a kind of normal-temperature nano composite getter, which is not necessarily to activated at, uses
It is convenient, safety and environmental protection nonhazardous, and haveing excellent performance, at normal temperature can residual gas in efficient absorption vacuum heat-insulating plate,
Good vacuum environment in plate is maintained, the service life of VIP is extended.
The invention provides the following technical scheme:
A kind of normal-temperature nano composite getter is alkaline earth oxide, transition metal oxide and rare earth oxide
The mixture of composition, the alkaline earth oxide are calcium oxide, and rare earth oxide is cerium oxide, and transition metal oxide is
The mixture that palladium oxide, titanium dioxide and other metal oxides are constituted, other metal oxides are selected from copper oxide, oxidation
One or more of cobalt and nickel oxide.
Further, the calcium oxide is nano active lime powder, and specific surface area is greater than 10m2/ g, apparent density
Less than 0.5g/cm3, shared weight ratio is greater than 95% in total getter.Nano active lime powder is nanoscale
Grain aggregate, porosity and looseness between particle surface and particle, large specific surface area, chemical activity is strong, and rate of water absorption is than common quotient
The high magnitude of industry calcium oxide, this is for the particularly significant (moisture inside VIP of micro-moisture environment under VIP inner vacuum state
Content is converted into 25 DEG C of relative humidity RH < 1%, so the getter of bigger serface, high activity is needed to carry out absorbing trace
Moisture).
Further, palladium oxide weight ratio shared in total getter is between 0.001%~0.01%.It is micro-
The palladium oxide of amount can significantly improve nano combined getter absorption H2With the ability of the reducibility gas such as CO.Due to copper oxide,
Cobalt oxide and nickel oxide etc. have the ability of the transition metal oxide absorbing and reducing gas at normal temperature of oxidisability very weak,
It generally requires and is heated at least 150 DEG C or more, VIP interior gas amount is few in addition, so improving oxygen by addition palladium oxide
The ability of the property changed transition metal oxide absorbing and reducing gas.In addition, the additive amount of palladium oxide is considerably less, increase material cost
It is few.
Further, titanium dioxide weight ratio shared in total getter is between 0.1%~1%, powder
The partial size at end is less than 100nm, and specific surface area is greater than 50m2/g.The big specific surface area of nano-titanium dioxide is the mistake with oxidisability
It crosses metal oxide and carrier is provided, improve its adsorption activity.
Further, other metal oxides weight ratio shared in total getter is 0.05%~0.2%
Between, for the partial size of powder less than 10 μm, specific surface area is greater than 50m2/ g, apparent density are less than 0.2g/cm3.Copper oxide, oxidation
Cobalt and nickel oxide etc. have the ability of the transition metal oxide absorbing and reducing gas at normal temperature of oxidisability very weak, pass through
It is loaded on nano-carrier (nano-titanium dioxide in the present invention) and improves its chemical activity, adsorb the H in VIP2, CO with
And other organic gas with reproducibility.
Further, cerium oxide weight ratio shared in total getter is between 0.1%~1%, powder
Partial size less than 10 μm, specific surface area be greater than 50m2/ g, apparent density are less than 0.2g/cm3.Ceria oxide powder is nano-scale particle
Aggregate, porosity and looseness between particle surface and particle, large specific surface area can improve preferably with the mixture of titanium dioxide
The chemical activity of oxidisability transition metal oxide.
Further, the getter in the form of a powder sealed package in ventilative and not in the polymer pouches of powder leakage, powder
End cannot leak out from bag surface or edge sealing.
Further, the polymer pouches are the non-woven bag of PE, PP or PET material, using three while or 4 while seal
It is made, since getter is when being added in core material, core material generally have passed through high temperature drying and processing, it requires polymer material
It is able to bear high temperature of the short time no more than 150 DEG C.
Further, the getter being filled in polymer pouches, weight per package is 1~30g, in rectangular shape, wherein one
Edge lengths are 2~10cm, and another edge lengths are 2~15cm.
Further, getter of the present invention is in vacuum heat-insulating plate, the residual gas in baffle to be maintained in plate
Good vacuum environment is prolonged the service life with improving the heat-insulating property of vacuum heat-insulating plate.
The beneficial effects of the present invention are:
Oxidisability transition metal oxide absorbing and reducing can be improved by addition micro-oxidation palladium in the present invention at normal temperature
Property gas ability, be not necessarily to activated at；It is the transition metal of oxidisability by adding the nano-titanium dioxide of bigger serface
Oxide provides carrier and greatly improves the chemical activity of oxidisability transition metal oxide in conjunction with the use of cerium oxide；Again
In addition nano active lime powder improves the matching of micro-moisture environment under VIP inner vacuum state well
The adsorption efficiency of entire getter.
The getter rate of water absorption is higher, and air-breathing is more thorough, and aqueous vapor balance pressure is lower, being capable of effective CO absorption2, H2, CO with
And reproducibility organic gas, to O2Also there is certain adsorption effect.In addition, the getter also has safety and environmental protection, without toxic
Harmful substance, easy to use, the advantages such as price is low.
Detailed description of the invention
Fig. 1 is the structural schematic diagram after the nano combined getter packaging of the present invention, and 10 be polymer pouches, and 20 be getter powder
End；
Fig. 2 (a) and Fig. 2 (b) is the SEM image of nano active calcium oxide Yu common commercial calcium oxide respectively；
Fig. 3 is the comparison of nano active calcium oxide of the present invention Yu common commercial calcium oxide rate of water absorption；
Fig. 4 is the structural schematic diagram for having used the vacuum heat-insulating plate of getter and common dessicant of the present invention, and 1 is air-breathing
Agent, 2 be gas-barrier bag, and 3 be core material.
Specific embodiment
In order to be more clear the purpose of the present invention, technical scheme and beneficial effects, below with reference to specific embodiment into
Row detailed description.
Embodiment 1
Weigh purity be greater than 95%, the lime powder 100g of 325 mesh of fineness, then respectively weigh 0.2g nitric acid copper powders,
The palladium nitrate powder of the titania powder of 0.5g, the cerous nitrate powder of 1.5g and 0.02g, all pours into the beaker of 400ml
In, add deionized water 300ml, then uses magnetic stirrer 30min；It pours the mixture into alumina crucible, in oven
Middle drying, 130 DEG C of baking temperature, baking time is greater than 100h, then the mixture after drying is placed in the atmosphere of nitrogen protection
It is calcined in furnace, 600 DEG C of calcination temperature, time 2h, products therefrom is crushed under nitrogen atmosphere protection with pulverizer, this hair is obtained
Bright nano combined getter power (number 1#), wherein in finished product, the weight ratio of each component is calcium oxide: copper oxide: two
Titanium oxide: cerium oxide: palladium oxide=100:0.07:0.5:0.6:0.01；Under nitrogen atmosphere protection, which is pressed
It is packaged in the overlay film non-woven fabrics of PET material according to the every packet 10g of weight, having a size of wide 70mm, long 110mm, structural schematic diagram such as Fig. 1
It is shown.
In product preparation, when directly using various oxides, due to that can not be uniformly mixed, and it is unable to get nanometer
Grade product, thus, it adopts the technology that, is first uniformly mixed the soluble nitrate solution of copper, cerium, palladium, be then sintered into pair
The oxide answered, following embodiment use same process.
Embodiment 2
Weigh purity be greater than 95%, the lime powder 50g of 500 mesh of fineness, then respectively weigh 0.3g nitric acid copper powders,
The palladium nitrate powder of the titania powder of 0.5g, the cerous nitrate powder of 1.26g and 0.0055g, all pours into the burning of 250ml
In cup, add deionized water 150ml, then uses magnetic stirrer 25min；It pours the mixture into alumina crucible, roasting
It is dried in case, 130 DEG C of baking temperature, baking time is greater than 100h, then the mixture after drying is placed in the gas of argon gas protection
It is calcined in atmosphere furnace, 600 DEG C of calcination temperature, time 2h, products therefrom is crushed under argon atmosphere protection with pulverizer, this is obtained
The nano combined getter power of invention, wherein in finished product, the weight ratio of each component is calcium oxide: copper oxide: titanium dioxide:
Cerium oxide: palladium oxide=100:0.2:1:1:0.005；Under argon atmosphere protection, the getter power according to the every packet of weight
2g is packaged in the overlay film non-woven fabrics of PE material, having a size of wide 20mm, long 50mm.
Embodiment 3
It weighs purity and is greater than 95%, the lime powder 100g of 500 mesh of fineness, then weigh 0.182g nitric acid cobalt powder respectively
The palladium nitrate powder at end, the cerous nitrate powder of the titania powder of 0.5g, 1.26g and 0.01g, all pours into 400ml's
In beaker, add deionized water 300ml, then uses magnetic stirrer 30min；It pours the mixture into alumina crucible,
It is dried in oven, 130 DEG C of baking temperature, baking time is greater than 100h, and the mixture after drying is then placed in air atmosphere stove
Middle calcining, products therefrom is crushed under argon atmosphere protection with pulverizer, the present invention is obtained by 600 DEG C of calcination temperature, time 2h
Nano combined getter power, wherein in finished product, the weight ratio of each component is calcium oxide: cobalt oxide: titanium dioxide: oxidation
Cerium: palladium oxide=100:0.1:0.5:0.5:0.0046；Under argon atmosphere protection, the getter power according to the every packet of weight
15g is packaged in the overlay film non-woven fabrics of PE material, having a size of wide 100mm, long 120mm.
Embodiment 4
Weigh purity be greater than 95%, the lime powder 100g of 500 mesh of fineness, then respectively weigh 0.7g nitric acid nickel by powder,
The palladium nitrate powder of the titania powder of 0.5g, the cerous nitrate powder of 1.26g and 0.02g, all pours into the beaker of 400ml
In, add deionized water 300ml, then uses magnetic stirrer 30min；It pours the mixture into alumina crucible, in oven
Middle drying, 130 DEG C of baking temperature, baking time is greater than 100h, and then the mixture after drying is placed in air atmosphere stove and is forged
It burns, 580 DEG C of calcination temperature, time 2h, products therefrom is crushed under argon atmosphere protection with pulverizer, of the invention receive is obtained
The weight ratio of rice composite getter powder, each component is calcium oxide: nickel oxide: titanium dioxide: cerium oxide: palladium oxide=100:
0.2:0.5:0.5:0.01；Under argon atmosphere protection, which is packaged in PET material according to the every packet 20g of weight
Overlay film non-woven fabrics in, having a size of wide 100mm, long 150mm.
Comparative example 1 compares for convenience, prepares nano active lime powder according to the technique of embodiment 1.
It weighs purity and is greater than 95%, the lime powder 100g of 325 mesh of fineness pours into the beaker of 400ml, adds deionization
Water 300ml is dried, baking temperature 130 in an oven with being poured into alumina crucible after magnetic stirrer 30min
DEG C, baking time is greater than for 24 hours, and then mixture after drying is placed in the atmosphere furnace of nitrogen protection and is calcined, calcination temperature 600
DEG C, products therefrom is crushed under nitrogen atmosphere protection with pulverizer, obtains nano active lime powder, number by time 2h
For 2#.
Comparative example 2 weighs embodiment 1, and with calcium oxide raw material powder, material, number 3#, and production etc. are heavy every as a comparison
Wrap the contrast sample of 10g.
Test case 1 carries out Morphology analysis to the sample powder of comparative example 1 (2#) and comparative example 2 (3#), and table is compared in test
Area and rate of water absorption.
Fig. 2 (a) and Fig. 2 (b) is respectively the SEM image of 2# and 3# sample, from figure 2 it can be seen that the commercial oxidation of 3#
For calcium after activation processing, partial size reduces 100 times, and it is porous thin to become nanoscale from original micron-sized hard particles
The active calcium oxide (2#) of pine.The specific surface area of activation front and back is respectively 1.54m2/ g and 16.82m2/ g, specific surface area increase by one
A magnitude.Test results are shown in figure 3 for rate of water absorption, and the nano active calcium oxide rate of water absorption of 2# is than common commercial oxidation calcium
(3#) high magnitude, this is particularly significant for the absorption of micro-moisture under VIP inner vacuum state (due to other oxygen of addition
The amount relative activity calcium oxide of compound is fewer, and its in addition to calcium oxide is not observed in the SEM image of final finished getter
Its oxide, therefore compared with the SEM of the calcium oxide after activation and commercial oxidation calcium).
Test case 2 is added with 1 getter of embodiment (1#) and 2 desiccant of comparative example (3#) vacuum heat-insulating plate (VIP) (Fig. 4)
Production, thermal coefficient and ageing properties test.
Using glass fiber core material, yin-yang film barrier bag, respectively added with embodiment 1# getter and 3# desiccant production two
The VIP of seed type, and test the initial thermal conductivity coefficient of two kinds of VIP, be subsequently placed in 70 DEG C, accelerate in the environment of 90%RH it is old
Change test, the results are shown in Table 1.
1 VIP the performance test results of table
Seen from table 1, added with the VIP sample of 1# getter, initial thermal conductivity coefficient is slightly below the VIP sample added with 3# desiccant
Product, it is often more important that, behind aging 180 days of high temperature and humidity, only risen added with the VIP thermal coefficient of 1# getter
2.7mW/ (mK), and 9.6mW/ (mK) to 11.6mW/ (mK) is risen added with the VIP thermal coefficient of 3# desiccant,
Lost superinsulation effect.
It is clear that normal-temperature nano composite getter of the invention is applied in VIP, it being capable of residual gas effectively in adsorption plate
Body maintains good vacuum environment, improves its heat-insulating property, prolongs the service life.
Claims (10)
1. a kind of normal-temperature nano composite getter, which is characterized in that for alkaline earth oxide, transition metal oxide and dilute
The mixture of native oxide composition, the alkaline earth oxide is calcium oxide, and rare earth oxide is cerium oxide, transition metal
Oxide is the mixture that palladium oxide, titanium dioxide and other metal oxides are constituted, and other metal oxides are selected from oxygen
Change one or more of copper, cobalt oxide and nickel oxide.
2. a kind of normal-temperature nano composite getter as described in claim 1, which is characterized in that the calcium oxide is nano active
Lime powder, specific surface area are greater than 10m2/ g, apparent density are less than 0.5g/cm3, the shared weight in total getter
Than being greater than 95%.
3. a kind of normal-temperature nano composite getter as described in claim 1, which is characterized in that the palladium oxide is in total air-breathing
Shared weight ratio is between 0.001%~0.01% in agent.
4. a kind of normal-temperature nano composite getter as described in claim 1, which is characterized in that the titanium dioxide is in total suction
For shared weight ratio between 0.1%~1%, the partial size of powder is less than 100nm in gas agent, and specific surface area is greater than 50m2/g。
5. a kind of normal-temperature nano composite getter as described in claim 1, which is characterized in that other metal oxides exist
Shared weight ratio is between 0.05%~0.2% in total getter, and less than 10 μm, specific surface area is greater than the partial size of powder
50m2/ g, apparent density are less than 0.2g/cm3。
6. a kind of normal-temperature nano composite getter as described in claim 1, which is characterized in that the cerium oxide is in total air-breathing
Shared weight ratio is between 0.1%~1% in agent, and for the partial size of powder less than 10 μm, specific surface area is greater than 50m2/ g, pine dress
Density is less than 0.2g/cm3。
7. a kind of normal-temperature nano composite getter as described in claim 1~6 is any, which is characterized in that the getter with
In ventilative and not in the polymer pouches of powder leakage, powder cannot leak out the form sealed package of powder from bag surface or edge sealing.
8. a kind of normal-temperature nano composite getter as claimed in claim 7, which is characterized in that the polymer pouches be PE,
The non-woven bag of PP or PET material, using three while or 4 while seal and be made.
9. a kind of normal-temperature nano composite getter as claimed in claim 7, which is characterized in that the suction being filled in polymer pouches
Gas agent, weight per package is 1~30g, in rectangular shape, wherein an edge lengths are 2~10cm, another edge lengths are 2~15cm.
10. any normal-temperature nano composite getter as described in claim 1~6 and 8,9, which is characterized in that described
Getter is in vacuum heat-insulating plate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110918045A (en) * | 2019-12-10 | 2020-03-27 | 西华大学 | Normal-temperature air-suction composite material and product thereof |
| CN112604642A (en) * | 2020-11-24 | 2021-04-06 | 重庆再升科技股份有限公司 | Getter for vacuum insulation panel and preparation method thereof |
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