CN106256902B - A kind of LBL self-assembly process for fixation of microorganism - Google Patents
A kind of LBL self-assembly process for fixation of microorganism Download PDFInfo
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Abstract
The present invention relates to chemical wastewater treatment technical fields, more particularly to a kind of LBL self-assembly process for fixation of microorganism, the LBL self-assembly process for fixation of the microorganism is the following steps are included: the dilution of hyperbranched diazonium salt solution, the grafting of carrier, the LBL self-assembly immobilization of microbial immobilization and microorganism.Microorganism is fixed on polyurethane surface by the LBL self-assembly process for fixation of microorganism of the invention using hyperbranched diazonium salt as crosslinking agent, it does not need to pre-process carrier surface and microorganism, and the activity of microorganism is had no significant effect, have the characteristics that method is easy to operate, be swift in response, microbiological treatment is high-efficient after immobilization, and the degree of self assembly can be flexibly controlled, it is advantageously implemented industrialization.
Description
Technical field
The present invention relates to chemical wastewater treatment technical field more particularly to a kind of LBL self-assembly immobilization sides of microorganism
Method.
Background technique
With the industrial fast development in China, the ratio that wastewater from chemical industry accounts in China's sewage composition is increasing,
The industries such as petrochemical industry, process hides, papermaking, steel can generate a large amount of wastewater from chemical industry, and wastewater from chemical industry is high containing pollutant concentration, complicated component,
And it is most of containing eutrophy elements such as nitrogen phosphorus, serious water pollution can be caused by being directly discharged into water body.Pass through traditional activity
Sludge, not good enough to the treatment effect of wastewater from chemical industry, effluent quality is difficult to up to standard.
Phase early 1980s, immobilized microorganism technique start to be applied in sewage disposal process, and the technology is advantageous
In the concentration for improving microorganism in bioreactor, immobilized microorganism can resist the influence of adverse environment, and be conducive to
Separation of solid and liquid after reaction, time needed for shortening processing.
Common microorganism immobilization method has absorption method, investment, cross-linking method etc..Absorption method is by microorganism and to carry
The effects of Van der Waals force, hydrogen bond, covalent bond and ionic bond between body, is attached together, and this method is easy to operate, but micro- life
Object combine it is unstable, be easy to fall off.Investment is that microorganism is trapped in load using the effects of polymerization or ion network
In the porous network of body, to realize the fixation of microorganism, the microbial immobilized degree of this method is high, and materialization is stablized, and can be supported
The murder by poisoning of anti-harmful substance, the disadvantage is that the diffusional resistance between microorganism and matrix is big, and technique is more complex, and it is dirty to be not suitable for macromolecular
Contaminate the decomposition of substance.Cross-linking method is covalent using multi-functional groups such as aldehydes, amines as being formed between crosslinking agent and microorganism
The combination of key, by the flocculation granulating of microorganism itself, thus a kind of immobilization technology realized, the disadvantage is that medicament selection compared with
Difficulty, and crosslinking agent is costly.
Chinese invention patent application number 201410137361.0 discloses a kind of microorganism immobilization method, preparation cation
The Polyurethane carrier material that aperture is 30-60PPI is placed in 3%-10% hydrochloric acid solution and handles 15-24 by type polyurethane carrier
Hour；Using absorption method, by inoculated reactor in 25-35 DEG C heat preservation 6-12 hours, lactic acid bacteria raised growth is simultaneously adsorbed on
Polyurethane surface.It is introduced using polyurethane as the method for carrier fixation of microbe, but the microorganism of immobilization is easy to fall off,
And its is microbial immobilized inefficient.
Summary of the invention
Technical problem to be solved by the present invention lies in the deficiencies for overcoming the above-mentioned prior art, provide a kind of layer of microorganism
Layer self-assembled monolayer method utilizes hyperbranched diazonium salt using the hyperbranched diazonium salt of high reaction activity as crosslinking agent
Active function groups make polyurethane surface have the active function groups of diazonium salt, and then microorganism passes through the diazonium with polyurethane surface
Salt active function groups form covalent bond, so that microorganism is firmly fixed on polyurethane surface, repeat above step, realize
Microorganism is controllable the surface immobilized amount of Polyurethane carrier, to realize microorganism self-assembled monolayer layer by layer.
The main technical schemes that a kind of LBL self-assembly process for fixation of microorganism provided by the invention uses are as follows: including
Following steps:
(1) dilution of hyperbranched diazonium salt solution: the hyperbranched diazonium salt solution of a certain amount of volume is measured, is diluted with water to
50~100 times；
(2) grafting of carrier: at a certain temperature, carrier is immersed in the hyperbranched diazonium salt solution after dilution certain
Time；
(3) microbial immobilization: being taken out the carrier, cleaned up using water, is blown rapidly with the cold wind of certain temperature
It is dry；At a certain temperature, then by the carrier the not certain time in active microorganism solution is invaded；
(4) the LBL self-assembly immobilization of microorganism: being repeated in step 2 and step 3 at least once, completes entirely from group
Fill immobilization process.
A kind of LBL self-assembly process for fixation of microorganism provided by the invention uses following attached technical scheme:
The structural formula of hyperbranched diazonium salt is in the step 1
Wherein m is the number of iterations of chemical group in above-mentioned molecular formula brace.
The preparation method of hyperbranched diazonium salt includes the following steps: in the step 1
(1) N for being 1: 2 by molar ratio, N- (2- ethoxy) aniline is reacted with oxychloride generates N, N- (2- chloroethyl)
Aniline；
(2) molar ratio is reacted for 2: 1 4-aminobenzoic acid and N, N- (2- chloroethyl) aniline and replaces N, N-
(2- chloroethyl) aniline chlorine atom therein；
(3) then under the catalysis of sodium nitrite, sulfuric acid, acetic acid and dimethylformamide, the generation of above-mentioned steps 2 is produced
Object itself occurs polymerization reaction and generates the hyperbranched diazonium salt.
Immersion time of the carrier described in the step 2 in hyperbranched diazonium salt solution is 0.5-2h.
Immersion time of the carrier described in the step 3 in the active microorganism solution is 4-6h.
The temperature of submergence crosslinking of the carrier described in the step 2 in the hyperbranched diazonium salt solution is 2-4 DEG C.
The temperature that carrier described in the step 3 submerges absorption in the active microorganism is 4-8 DEG C.
The storage temperature of hyperbranched diazonium salt solution after the dilution is 2-4 DEG C.
The carrier is polyurethane.
The shape of the polyurethane is a height of 10-20mm square of length and width or cuboid.
LBL self-assembly is the method using layer-by-layer alternating deposit, by intermolecular weak interaction (such as electrostatic of each layer
Gravitation, hydrogen bond, coordinate bond etc.), so that layer and layer is spontaneously associated and forms structural integrity, performance stabilization, there is certain specific function
Molecule aggregate and supramolecular structure process.It is that one kind that the 1990s, fast development was got up is simple, multi-functional
Surface modification method, mainly it is more to prepare polyelectrolyte self assembly for the alternating deposit using charged substrate in oppositely charged
Tunic.
Diazonium salt be containing diazo salt, it is soluble easily in water, ionize, aqueous solution has very strong conductive capability,
It is the important initiator of one kind of material surface chemical modification.Hyperbranched diazonium salt due to its hyperbranched polymer architecture and
Polyfunctional group property makes it have potential use in microbial immobilized field.
Polyurethane is a kind of high-molecular organic material, and with large specific surface area, foam pores are more, and enabling capabilities are strong, property
The features such as matter is stablized, the application in terms of immobilized microorganism receive significant attention.
The beneficial effect of the LBL self-assembly process for fixation of microorganism of the invention is:
1) the LBL self-assembly process for fixation of microorganism of the invention will be micro- using hyperbranched diazonium salt as crosslinking agent
Biological fixation there is not the activity of microorganism on polyurethane surface, not needing to pre-process carrier surface and microorganism
It has a significant impact, has the characteristics that method is easy to operate, is swift in response, microbiological treatment is high-efficient after immobilization, and can spirit
The degree of control self assembly living, is advantageously implemented industrialization.
2) in the LBL self-assembly process for fixation of microorganism of the invention in hyperbranched diazonium salt containing a large amount of double bonds and
Phenyl ring, have rigid structure, form certain steric hindrance, as crosslinking agent can keep a part of active group inwardly with load
Precursor reactant, another part active group is outward and microbial reaction.
3) the LBL self-assembly process for fixation of microorganism of the invention passes through multiple LBL self-assembly, dissaving polymer
It can be cross-linked with each other into tridimensional network between the microorganism of its fixation, microorganism can be further fixed, improve microorganism
Immobilization efficiency.
4) diazonium contained in hyperbranched diazonium salt used in the LBL self-assembly process for fixation of microorganism of the invention
Group has high reaction activity, adsorption efficiency height and effect stability；And this method can be applied to the carrier of a variety of unlike materials
On, universality is good.
Detailed description of the invention
Fig. 1 is the schematic diagram of the LBL self-assembly process for fixation of microorganism of the invention.
1- polyurethane, the hyperbranched diazonium salt of 2-,
3- microorganism.
Specific embodiment
Below in conjunction with attached drawing, invention is further described in detail.
As shown in Figure 1, the LBL self-assembly process for fixation of microorganism of the present invention, includes the following steps:
(1) dilution of hyperbranched diazonium salt solution: the hyperbranched diazonium salt solution of a certain amount of volume is measured, is diluted with water to
It 50~100 times, is then stored at a temperature of 2-4 DEG C, to guarantee the stability of hyperbranched diazonium salt；Of the invention is hyperbranched heavy
Contain a large amount of double bonds and phenyl ring in nitrogen salt, there is rigid structure, form certain steric hindrance, one can be kept as crosslinking agent
Amount of activated group is inwardly reacted with carrier, and another part active group is outward and microbial reaction.
(2) at 2-4 DEG C, polyurethane the grafting of carrier: is immersed in 0.5- in the hyperbranched diazonium salt solution after dilution
2h；
(3) microbial immobilization: being taken out the polyurethane, cleaned up using water, rapid with the cold wind of certain temperature
Drying；4-8 DEG C at a temperature of, then by the polyurethane soaking in active microorganism solution 4-6h, with reach saturation absorption.
(4) the LBL self-assembly immobilization of microorganism: being repeated in step 2 and step 3 at least once, completes entirely from group
Fill immobilization process；The LBL self-assembly process for fixation of microorganism of the invention passes through multiple LBL self-assembly, hyperbranched poly
Tridimensional network can be cross-linked with each other between object and its microorganism fixed by closing, and can be further fixed microorganism, be improved micro-
The immobilization efficiency of biology.
The LBL self-assembly process for fixation of microorganism of the invention using hyperbranched diazonium salt as crosslinking agent by micro- life
Object is fixed on polyurethane surface, does not need to pre-process polyurethane surface and microorganism, and is not had to the activity of microorganism
It has a significant impact, has the characteristics that method is easy to operate, is swift in response, microbiological treatment is high-efficient after immobilization, and can spirit
The degree of control self assembly living, is advantageously implemented industrialization.
The shape of above-mentioned polyurethane is a height of 10-20mm square of length and width or cuboid.
Embodiment 1
The LBL self-assembly process for fixation of microorganism of the invention, includes the following steps:
(1) dilution of hyperbranched diazonium salt solution: the hyperbranched diazonium salt solution of a certain amount of volume is measured, is diluted with water to
It 50 times, is then stored at a temperature of 2 DEG C, to guarantee the stability of hyperbranched diazonium salt；
(2) at 4 DEG C, polyurethane the grafting of carrier: is immersed in 0.5h in the hyperbranched diazonium salt solution after dilution；
(3) microbial immobilization: being taken out the polyurethane, cleaned up using water, is dried up rapidly with 1 DEG C of cold wind；4
At a temperature of DEG C, then by the polyurethane soaking in active microorganism solution 6h, with reach saturation absorption.
(4) the LBL self-assembly immobilization of microorganism: being repeated in step 2 and step 3 five times, and it is solid to complete entire self assembly
Surely change process.
Polyurethane after above-mentioned immobilization is put into progress bio-film colonization experiment in aerobic reaction tank, it is dense in aerobic tank sludge
In the case that degree is 3.5g/L, it is only necessary to which the biofilm of polyurethane surface and inside can be completed in 2d, takes certain COD (following
Abbreviation COD) it intakes for the wastewater from chemical industry conduct of 850mg/L, 93% or more can achieve to the removal rate of COD, water outlet COD is lower than
80mg/L.After carrying out analysis comparison by the polyurethane to LBL self-assembly immobilized microorganism and the polyurethane without immobilization
It was found that the polyurethane after hyperbranched diazonium salt crosslinking LBL self-assembly is fixed, fixing biomass can be improved 40%.
Embodiment 2
The LBL self-assembly process for fixation of microorganism of the invention, includes the following steps:
(1) dilution of hyperbranched diazonium salt solution: the hyperbranched diazonium salt solution of a certain amount of volume is measured, is diluted with water to
It 100 times, is then stored at a temperature of 4 DEG C, to guarantee the stability of hyperbranched diazonium salt；
(2) at 2 DEG C, polyurethane the grafting of carrier: is immersed in 2h in the hyperbranched diazonium salt solution after dilution；
(3) microbial immobilization: being taken out the polyurethane, cleaned up using water, is dried up rapidly with 4 DEG C of cold wind；8
At a temperature of DEG C, then by the polyurethane soaking in active microorganism solution 4h, with reach saturation absorption.
(4) the LBL self-assembly immobilization of microorganism: being repeated in step 2 and step 3 eight times, and it is solid to complete entire self assembly
Surely change process.
Polyurethane after above-mentioned immobilization is put into progress bio-film colonization experiment in aerobic reaction tank, it is dense in aerobic tank sludge
In the case that degree is 4g/L, it is only necessary to which the biofilm of polyurethane surface and inside can be completed in 3d, and taking certain COD is the change of 800mg/L
Work waste water can achieve 90% or more as water inlet, to the removal rate of COD, and water outlet COD is lower than 80mg/L.By to layer by layer from group
The polyurethane of dress immobilized microorganism and the polyurethane without immobilization are found after carrying out analysis comparison, by hyperbranched diazonium salt
It is crosslinked the polyurethane after LBL self-assembly is fixed, fixing biomass can be improved 35%.
Embodiment 3
The LBL self-assembly process for fixation of microorganism of the invention, includes the following steps:
(1) dilution of hyperbranched diazonium salt solution: the hyperbranched diazonium salt solution of a certain amount of volume is measured, is diluted with water to
It 80 times, is then stored at a temperature of 3 DEG C, to guarantee the stability of hyperbranched diazonium salt；
(2) at 3 DEG C, polyurethane the grafting of carrier: is immersed in 1h in the hyperbranched diazonium salt solution after dilution；
(3) microbial immobilization: being taken out the polyurethane, cleaned up using water, is dried up rapidly with 3 DEG C of cold wind；6
At a temperature of DEG C, then by the polyurethane soaking in active microorganism solution 5h, with reach saturation absorption.
(4) the LBL self-assembly immobilization of microorganism: being repeated in step 2 and step 3 seven times, and it is solid to complete entire self assembly
Surely change process.
Polyurethane after above-mentioned immobilization is put into progress bio-film colonization experiment in aerobic reaction tank, it is dense in aerobic tank sludge
In the case that degree is 3.8g/L, it is only necessary to which the biofilm of polyurethane surface and inside can be completed in 3d, and taking certain COD is 900mg/L's
Wastewater from chemical industry can achieve 95% or more as water inlet, to the removal rate of COD, and water outlet COD is lower than 80mg/L.By to layer by layer from
The polyurethane of assembling immobilized microorganism and the polyurethane without immobilization are found after carrying out analysis comparison, by hyperbranched diazonium
Salt is crosslinked the polyurethane after LBL self-assembly is fixed, and fixing biomass can be improved 38%.
Embodiment 4
The LBL self-assembly process for fixation of microorganism of the invention, includes the following steps:
(1) dilution of hyperbranched diazonium salt solution: the hyperbranched diazonium salt solution of a certain amount of volume is measured, is diluted with water to
It 70 times, is then stored at a temperature of 3.5 DEG C, to guarantee the stability of hyperbranched diazonium salt；
(2) at 3 DEG C, polyurethane the grafting of carrier: is immersed in 1.5h in the hyperbranched diazonium salt solution after dilution；
(3) microbial immobilization: being taken out the polyurethane, cleaned up using water, is dried up rapidly with 2 DEG C of cold wind；7
At a temperature of DEG C, then by the polyurethane soaking in active microorganism solution 4.5h, with reach saturation absorption.
(4) the LBL self-assembly immobilization of microorganism: being repeated in step 2 and step 30 times, and it is solid to complete entire self assembly
Surely change process.
Polyurethane after above-mentioned immobilization is put into progress bio-film colonization experiment in aerobic reaction tank, it is dense in aerobic tank sludge
In the case that degree is 3g/L, it is only necessary to which the biofilm of polyurethane surface and inside can be completed in 2d, and taking certain COD is the change of 750mg/L
Work waste water can achieve 95% or more as water inlet, to the removal rate of COD, and water outlet COD is lower than 80mg/L.By to layer by layer from group
The polyurethane of dress immobilized microorganism and the polyurethane without immobilization are found after carrying out analysis comparison, by hyperbranched diazonium salt
It is crosslinked the polyurethane after LBL self-assembly is fixed, fixing biomass can be improved 36%.
Embodiment 5
The LBL self-assembly process for fixation of microorganism of the invention, includes the following steps:
(1) dilution of hyperbranched diazonium salt solution: the hyperbranched diazonium salt solution of a certain amount of volume is measured, is diluted with water to
It 60 times, is then stored at a temperature of 4 DEG C, to guarantee the stability of hyperbranched diazonium salt；
(2) at 4 DEG C, polyurethane the grafting of carrier: is immersed in 0.5h in the hyperbranched diazonium salt solution after dilution；
(3) microbial immobilization: being taken out the polyurethane, cleaned up using water, is dried up rapidly with cold wind；At 6 DEG C
At a temperature of, then by the polyurethane soaking in active microorganism solution 5.5h, with reach saturation absorption.
(4) the LBL self-assembly immobilization of microorganism: being repeated in step 2 and step 3 six times, and it is solid to complete entire self assembly
Surely change process.
Polyurethane after above-mentioned immobilization is put into progress bio-film colonization experiment in aerobic reaction tank, it is dense in aerobic tank sludge
In the case that degree is 4g/L, it is only necessary to which the biofilm of polyurethane surface and inside can be completed in 3d, and taking certain COD is the change of 950mg/L
Work waste water can achieve 95% or more as water inlet, to the removal rate of COD, and water outlet COD is lower than 80mg/L.By to layer by layer from group
The polyurethane of dress immobilized microorganism and the polyurethane without immobilization are found after carrying out analysis comparison, by hyperbranched diazonium salt
It is crosslinked the polyurethane after LBL self-assembly is fixed, fixing biomass can be improved 38%.
Embodiment 6
The LBL self-assembly process for fixation of microorganism of the invention, includes the following steps:
(1) dilution of hyperbranched diazonium salt solution: the hyperbranched diazonium salt solution of a certain amount of volume is measured, is diluted with water to
It 80 times, is then stored at a temperature of 4 DEG C, to guarantee the stability of hyperbranched diazonium salt；
(2) at 3 DEG C, polyurethane the grafting of carrier: is immersed in 1h in the hyperbranched diazonium salt solution after dilution；
(3) microbial immobilization: being taken out the polyurethane, cleaned up using water, is dried up rapidly with cold wind；At 6 DEG C
At a temperature of, then by the polyurethane soaking in active microorganism solution 5h, with reach saturation absorption.
(4) the LBL self-assembly immobilization of microorganism: it is repeated in step 2 and step 3 15 times, completes entire self assembly
Immobilization process.
Polyurethane after above-mentioned immobilization is put into progress bio-film colonization experiment in aerobic reaction tank, it is dense in aerobic tank sludge
In the case that degree is 3.8g/L, it is only necessary to which the biofilm of polyurethane surface and inside can be completed in 3d, and taking certain COD is 900mg/L's
Wastewater from chemical industry can achieve 95% or more as water inlet, to the removal rate of COD, and water outlet COD is lower than 80mg/L.By to layer by layer from
The polyurethane of assembling immobilized microorganism and the polyurethane without immobilization are found after carrying out analysis comparison, by hyperbranched diazonium
Salt is crosslinked the polyurethane after LBL self-assembly is fixed, and fixing biomass can be improved 37%.
Embodiment 7
The LBL self-assembly process for fixation of microorganism of the invention, includes the following steps:
(1) dilution of hyperbranched diazonium salt solution: the hyperbranched diazonium salt solution of a certain amount of volume is measured, is diluted with water to
It 90 times, is then stored at a temperature of 3.5 DEG C, to guarantee the stability of hyperbranched diazonium salt；
(2) at 3 DEG C, polyurethane the grafting of carrier: is immersed in 1h in the hyperbranched diazonium salt solution after dilution；
(3) microbial immobilization: being taken out the polyurethane, cleaned up using water, is dried up rapidly with cold wind；At 7 DEG C
At a temperature of, then by the polyurethane soaking in active microorganism solution 4h, with reach saturation absorption.
(4) the LBL self-assembly immobilization of microorganism: being repeated in step 2 and step 30 times, and it is solid to complete entire self assembly
Surely change process.
Polyurethane after above-mentioned immobilization is put into progress bio-film colonization experiment in aerobic reaction tank, it is dense in aerobic tank sludge
In the case that degree is 3.3g/L, it is only necessary to which the biofilm of polyurethane surface and inside can be completed in 2.5d, and taking certain COD is 800mg/L
Wastewater from chemical industry as water inlet, 90% or more can achieve to the removal rate of COD, water outlet COD is lower than 80mg/L.By to layer by layer
The polyurethane of self-assembled monolayer microorganism and polyurethane without immobilization are found after carrying out analysis comparison, by hyperbranched heavy
Nitrogen salt is crosslinked the polyurethane after LBL self-assembly is fixed, and fixing biomass can be improved 36%.
Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not protects model to the present invention
The limitation enclosed, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art are not
Need to make the creative labor the various modifications or changes that can be made still within protection scope of the present invention.
Claims (6)
1. a kind of LBL self-assembly process for fixation of microorganism, which comprises the steps of:
(1) dilution of hyperbranched diazonium salt solution: measuring the hyperbranched diazonium salt solution of a certain amount of volume, it is diluted with water to 50~
100 times；
(2) grafting of carrier: at a certain temperature, carrier is immersed in a timing in the hyperbranched diazonium salt solution after dilution
Between；
(3) microbial immobilization: being taken out the carrier, cleaned up using water, is dried up rapidly with the cold wind of certain temperature；?
Under certain temperature, then the carrier is immersed in certain time in active microorganism solution；
(4) the LBL self-assembly immobilization of microorganism: being repeated in step (2) and step (3) at least once, completes entirely from group
Fill immobilization process；
The structural formula of hyperbranched diazonium salt is in the step (1)
Wherein m is the number of iterations of chemical group in above-mentioned molecular formula brace；
The preparation method of hyperbranched diazonium salt includes the following steps: in the step (1)
(11) N for being 1:2 by molar ratio, N- (2- ethoxy) aniline is reacted with oxychloride generates N, N- (2- chloroethyl) benzene
Amine；
(12) 4-aminobenzoic acid and N for being 2:1 by molar ratio, N- (2- chloroethyl) aniline react and replace N, N- (2-
Chloroethyl) aniline chlorine atom therein；
(13) then under the catalysis of sodium nitrite, sulfuric acid, acetic acid and dimethylformamide, the generation of above-mentioned steps (12) is produced
Object itself occurs polymerization reaction and generates the hyperbranched diazonium salt；
Immersion time of the carrier in hyperbranched diazonium salt solution described in the step (2) is 0.5-2h；
Immersion time of the carrier in the active microorganism solution described in the step (3) is 4-6h.
2. the LBL self-assembly process for fixation of microorganism as described in claim 1, it is characterised in that: in the step (2)
The temperature of submergence crosslinking of the carrier in the hyperbranched diazonium salt solution is 2-4 DEG C.
3. the LBL self-assembly process for fixation of microorganism as described in claim 1, it is characterised in that: in the step (3)
The temperature that the carrier submerges absorption in the active microorganism is 4-8 DEG C.
4. the LBL self-assembly process for fixation of microorganism as claimed in any one of claims 1-3, it is characterised in that: described
The storage temperature of hyperbranched diazonium salt solution after dilution is 2-4 DEG C.
5. the LBL self-assembly process for fixation of microorganism as claimed in any one of claims 1-3, it is characterised in that: described
Carrier is polyurethane.
6. the LBL self-assembly process for fixation of microorganism as claimed in claim 5, spy are: the shape of the polyurethane
For a height of 10-20mm square of length and width or cuboid.
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