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Viscoelastic Solid-Repellent Coatings For Extreme Water Saving and Global Sanitation
Viscoelastic Solid-Repellent Coatings For Extreme Water Saving and Global Sanitation
https://doi.org/10.1038/s41893-019-0421-0
Water scarcity threatens over half of the world’s population, yet over 141 billion litres of fresh water are used globally each day
for toilet flushing. This is nearly six times the daily water consumption of the population in Africa. The toilet water footprint is
so large primarily because large volumes of water are necessary for the removal of human faeces; human faeces is viscoelastic
and sticky in nature, causing it to adhere to conventional surfaces. Here, we designed and fabricated the liquid-entrenched
smooth surface (LESS)—a sprayable non-fouling coating that can reduce cleaning water consumption by ~90% compared with
untreated surfaces due to its extreme repellency towards liquids, bacteria and viscoelastic solids. Importantly, LESS-coated
surfaces can repel viscoelastic solids with dynamic viscosities spanning over nine orders of magnitude (that is, three orders of
magnitude higher than has previously been reported for other repellent materials). With an estimated 1 billion or more toilets
and urinals worldwide, incorporating LESS coating into sanitation systems will have significant implications for global sanita-
tion and large-scale wastewater reduction for sustainable water management.
W
ater shortage is one of today’s most pressing global orders of magnitude higher than was previously reported for other
issues1. In 2016, 4 billion people in the world faced severe repellent materials. To our knowledge, no state-of-the-art liquid
water scarcity2. With the growing world population, repellent surfaces have shown repellency against viscoelastic solids
fresh water supply continues to be in high demand, with typical con- with dynamic viscosity higher than ~100 Pa s (refs. 19–26).
sumption ranging from everyday household to industrial activities3. LESS consists of a nanoscopically smooth solid surface that is
To address the water shortage issue, mainstream research has been functionalized with molecularly grafted polymers that stabilize a
focused on finding new methods for sourcing fresh water, such as thin layer of lubricant through intermolecular forces. In addition,
water desalination and treatment4–6, and techniques for harvesting LESS can be applied onto various hydrophilic surfaces (for exam-
water from air7–10. Methods for reducing water waste by minimizing ple, ceramic, vitreous china, carbon steel, and so on) and complex
wastewater generation from daily household and industrial activi- geometries within minutes under ambient conditions. Additionally,
ties, such as toilet flushing, have received relatively less attention. we have shown that LESS can maintain non-stickiness towards
In the United States, toilet flushing accounts for 24% of all indoor human faeces, outperforming other commercially available mate-
domestic wastewater-producing activities, and is the largest con- rials. We have further demonstrated that LESS possesses excellent
tributor of indoor household wastewater production11. Globally, it anti-biofouling properties, which could reduce the use of aggressive
is estimated that over 141 billion litres of water—nearly six times the chemicals currently used for sterilization. For a standard toilet using
daily water consumption of the entire population in Africa12—are 1.6 gallons flush−1 (~6 l flush−1), our characterization and analysis
used each day for toilet flushing alone13. A number of approaches show that every 1 ml of LESS coating fluid could potentially save
have been proposed to reduce fresh water consumption for toilet >1,000 l of water. Our coating is highly scalable and can easily be
flushing that range from the use of rainwater for flushing14 to the incorporated into used or existing ceramic- and metal-based toilets
use of self-contained dry toilets15. Owing to a great variety of com- and urinals to improve global sanitation and reduce wastewater
plex factors, such as local environment16, resource availability17 and production—a challenge that is listed as one of the 17 Sustainable
user preference18, none of these approaches can completely address Development Goals by the United Nations (that is, clean water
the water consumption issue. A relatively unexplored approach is and sanitation).
to engineer the material interface of toilet surfaces to significantly
weaken the adhesion of human faeces and urine in order to reduce Results and discussion
the amount of flushing water for waste removal. Our LESS coatings have been designed through interfacial adhesion
Here, we report the design, fabrication and performance (relating and thermodynamic analyses to effectively repel liquid, bacteria
to sanitation and water reduction) of a liquid-entrenched smooth and viscoelastic solids, and have been characterized under relevant
surface (LESS)—a sprayable, multifunctional surface coating that experimental conditions related to sanitation and water conserva-
can reduce cleaning water consumption by ~90% compared with an tion applications.
uncoated surface. The LESS is designed to repel aqueous fluids, bac-
teria and viscoelastic solids with dynamic viscosities spanning over Design criteria of LESS. Reducing the adhesion between viscoelas-
nine orders of magnitude (that is, from ~10−3 to ~105 Pa s)—three tic solid and substrate surfaces would require lowering the work of
1
Department of Mechanical Engineering, The Pennsylvania State University, University Park, PA, USA. 2Materials Research Institute, The Pennsylvania
State University, University Park, PA, USA. 3Department of Materials Science and Engineering, The Pennsylvania State University, University Park, PA, USA.
4
Centre for Competitive Creative Design, Cranfield University, Cranfield, UK. 5Department of Biomedical Engineering, The Pennsylvania State University,
University Park, PA, USA. 6These authors contributed equally: Lin Wang, Nan Sun. *e-mail: tswong@psu.edu
1.3 nm
Fig. 1 | Fabrication of LESS. a, Schematic showing the two-step spray-coating process to form the LESS coating. The molecularly grafted polymer layer
creates chemical affinity to the lubricant. b, Optical images showing the individual coating processes on glass. The lubricant used was silicone oil,
and the blue testing liquid was dyed water.
adhesion, wa. Specifically, the work of adhesion can be expressed Fabrication and characterization of LESS. Based on these design
as wa = R(γ13 + γ23 − γ12), which can be further simplified by the criteria, we have developed a number of LESS coatings for silica-
Girifalco and Good equation27 as wa = 2R(γ13 × γ23)1/2, where R is sur- based materials, such as glass, silicon, china, and so on. These
face roughness, defined as the ratio between apparent and projected substrates were chosen based on their inherent smoothness (with
surface areas of the solid substrate, and γij is the interfacial energy Ra = ~1 nm) and their hydroxyl group availability, which made
at the i–j interface, and 1, 2 and 3 refer to the solid substrate, visco- surface functionalization facile36. We further functionalized these
elastic solid and air, respectively. Therefore, minimizing wa can be surfaces with dimethyldimethoxysilane to create a polydimeth-
achieved: (1) physically by reducing the surface roughness, R; and ylsiloxane (PDMS)-grafted chemical layer (γ13 = ~21 mJ m−2). In
(2) chemically by reducing the interfacial energies of the underlying addition, silicone oil was chosen as the lubricating fluid due to its
solid–air interface (γ13) and the viscoelastic solid–air interface (γ23) strong chemical affinity towards the PDMS-grafted surfaces, as well
simultaneously. as its excellent chemical stability37 and low environmental impact38.
Accordingly, we designed LESS based on the above physical and Furthermore, our calculations of spreading parameters and
chemical criteria. To reduce wa physically, a nanoscopically smooth Hamaker constants A have shown that this specific material com-
solid substrate was used (that is, R = ~1), since the total work of bination (that is, silicone oil and the PDMS-grafted surface) satis-
adhesion between two surfaces is directly proportional to their fies the requirement for a stable lubricant film formation (that is,
respective contact area, which could be significantly increased by S ≥ 0 and A > 0; Supplementary Note 3 and Supplementary Tables 1
the presence of roughness27. Specifically, Dahlquist28 showed experi- and 2), which are consistent with our experimental observations
mentally that when the storage modulus of an adherent material is (Supplementary Video 1).
below a certain critical value (that is, typically 0.3 MPa), the mate- Our LESS can be formed on a range of substrates through a two-
rial will begin to flow and form conformal contact with the surface step spray-coating process (Fig. 1 and Supplementary Video 2).
roughness of the adherent, regardless of the applied pressure. Our The first step generates a covalently bonded chemical layer on the
adhesion measurements have further confirmed that the surface substrate, and the second step creates an overcoat lubricant layer.
adhesion of viscoelastic solids increases with the surface rough- Before the surface functionalization, the surfaces need to be rinsed
ness (with average roughness, Ra ranges from 0.87 ± 0.06 nm to with isopropanol and deionized water to remove surface contami-
4.12 ± 0.26 µm; Supplementary Note 1), indicating that a relatively nants and expose the hydroxyl groups. Once the surface is clean and
smooth surface is important in reducing surface adhesion with dry, a solution containing dimethyldimethoxysilane is sprayed onto
viscoelastic solids. the surface under ambient conditions, allowing these molecules to
Reducing wa chemically can be achieved conventionally by react with the hydroxyl groups, and forming a covalently bonded
functionalizing a smooth solid substrate with a low surface PDMS-grafted layer on the substrate. After rinsing with ethanol
energy coating (that is, reducing γ13), or by adding lubricant to and isopropanol to remove the excess PDMS, the silanized substrate
be absorbed by viscoelastic solid29 (that is, reducing γ23). To fur- then becomes hydrophobic and can repel both water and alkanes26.
ther reduce wa, both γ13 and γ23 can be reduced simultaneously This step is modified from the method developed by Wang and
by creating a stable lubricant layer between the substrate and the McCarthy26 without the need for oxygen plasma treatment, which
viscoelastic solid (Supplementary Fig. 1a and Supplementary allows for a simpler and more scalable fabrication process. The
Note 2). Unlike wetting of a liquid film on rough solids30,31, formation of the new surface functional group was confirmed by
achieving super-wetting of a liquid film on a smooth surface is X-ray photoelectron spectroscopy measurements showing the for-
more challenging and requires the use of intermolecular forces mation of Si–O bonds associated with dimethyldimethoxysilane
to stabilize the thin liquid film24,32. Thermodynamically, to (Supplementary Fig. 2). The thickness of the PDMS-grafted layer
achieve this condition, the lubricant should have a non-nega- was estimated to be ~1.3 nm from the X-ray photoelectron spectros-
tive spreading parameter S on the solid substrate and a positive copy measurement39 (Supplementary Note 4), and the water contact
disjoining pressure П(e)33–35 in the presence of both air and the angle hysteresis of the surface is 6.8 ± 0.5° (Supplementary Table 3).
foreign immiscible liquid of interest (that is, S ≥ 0 and П(e) > 0), In the second step, the PDMS-grafted surface is preferentially
respectively (Methods). wetted by silicone oil, forming a stable lubricating layer. The thickness
Before
Faeces impact
Rinsing
b
Regime 1: Regime 2:
Conventional surfaces
Fig. 2 | Overview of state-of-the-art liquid and viscoelastic solid repellent surfaces. a, Schematic and optical images showing the comparison of adhesion
between viscoelastic solids and different engineered surfaces, including (left to right) an uncoated glass, a superhydrophobic glass, a PDMS-grafted
glass, a SLIPS-coated glass and a LESS-coated glass. The superhydrophobic glass was created using a commercially available superhydrophobic coating
(NeverWet). The SLIPS-coated glass had an underlying surface roughness of ~1 µm. Synthetic faeces with a solid content percentage of 30% (dynamic
viscosity = ~2,406 Pa s) was used in these experiments. b, Plot showing the reported dynamic viscosity range of liquids and viscoelastic solids that can be
repelled by the state-of-the-art liquid repellent surfaces and the LESS-coated surface.
of the lubricant can be controlled by either spin coating or spray (Fig. 2 and Supplementary Video 4)19–26. Furthermore, we have dem-
coating. In our experiments, the typical thickness of the lubricant onstrated that our LESS coating can be applied onto complex geome-
was controlled to be ~1 µm to ~10 µm. tries under room conditions without the use of advanced equipment.
Distinct from other fabrication methods to create liquid-infused As a demonstration, we applied LESS coating onto a toilet bowl
slippery surfaces, which generally take on the order of hours to surface through a spray-coating process. This coating could repel
complete32,40–42, our two-step fabrication process takes less than both dyed water and synthetic faeces more effectively than a com-
~5 min (Supplementary Video 2), and can be applied to other mercial hydrophobic glaze-coated toilet (Fig. 3 and Supplementary
hydrophilic materials such as ceramic, carbon steel, titanium, Videos 5 and 6).
and so on (Supplementary Video 3 and Supplementary Table 4).
LESS can effectively repel rainwater, soapy water and hard water Adhesion of LESS against viscoelastic synthetic faeces. To quan-
(Supplementary Note 5, Supplementary Fig. 3 and Supplementary tify the anti-adhesion performance of the LESS-coated surface, we
Tables 5–8), as well as synthetic faeces (Fig. 2a, Methods and performed surface adhesion measurements using synthetic faeces
Supplementary Video 2) with dynamic viscosities spanning over against other control surfaces. We prepared synthetic faeces with an
nine orders of magnitude (that is, from ~10−3 to ~105 Pa s) com- organic solid content similar to that of human faeces43 for adhesion
pared with other control surfaces including an uncoated surface, characterization (Methods and Supplementary Tables 9 and 10). The
a superhydrophobic surface, a PDMS-grafted smooth surface and solid contents of the synthetic faeces ranged from 10–60 wt%, which
a slippery liquid-infused porous surface (SLIPS)-coated surface corresponds to a storage modulus of between ~1 Pa (~10 wt%) and
Dyed water
Synthetic faeces
Fig. 3 | Comparison of liquid and synthetic faeces repellency between a state-of-the-art commercial hydrophobic glaze-coated toilet (SloanTec
hydrophobic glaze) and a LESS-coated toilet. Dyed water and synthetic faeces at 30% solid content were used in these tests. The thin arrows indicate the
sliding direction of the dyed water droplets. Scale bars: 5 cm. See also Supplementary Videos 5 and 6 for details.
~105 Pa (~60 wt%) (Supplementary Fig. 4). These values closely stresses generated by these flows range from 0.093 Pa (at 1 gal-
emulate those of fresh human faeces44,45. lon min−1) to 0.60 Pa (at 2.5 gallons min−1), which are similar to
First, we investigated the importance of a stable lubricant layer those of typical toilets (that is, ~0.11 to ~0.78 Pa47; Supplementary
for reducing surface adhesion. The control surfaces in these tests Note 6 and Supplementary Table 11). To simulate the adhesion of
included uncoated bare glass with and without lubrication of silicone faeces to toilet surfaces during defecation, we dropped the syn-
oil, and PDMS-grafted glass. We normalized the work of debonding thetic faeces (~5 g) from a height of ~400 mm onto the test surfaces
of the synthetic faeces on lubricated surfaces (lubricated glass and at a tilting angle of 45°. We then put the surfaces inside our open-
LESS) to that of the uncoated bare glass. Our results showed that channel flow system to determine the amount of water required
lubrication on bare glass can reduce the surface adhesion by ~41% to completely remove the faeces and their residues (Methods and
for synthetic faeces with 40% solid content (that is, the stickiest Supplementary Fig. 6). We verified the complete removal of the fae-
sample in the test). In comparison, grafted-PDMS glass can reduce ces residues using fluorescent trace dye, which was mixed with the
the surface adhesion by ~75%, while the LESS coating can reduce synthetic faeces during our tests (Supplementary Fig. 7). Compared
the adhesion by ~90% (Supplementary Fig. 1b). These experimen- with uncoated glass surfaces, LESS-coated surfaces reduced water
tal results are consistent with the predictions of work of adhesion, consumption to clean the surface by up to 90% for various synthetic
showing up to 46% reduction on lubricated glass, 74% reduction faeces at different solid contents (Fig. 4b,c). We also conducted sim-
on silanized glass and 86% reduction on LESS-coated glass com- ilar characterizations on SLIPS samples and found that the water
pared with untreated glass, respectively (Supplementary Note 2). consumption increased with increasing underlying substrate rough-
Our results indicate that the presence of a stable lubricating layer on ness—a trend consistent with the observations in the adhesion tests
the underlying solid substrate is critical to reduce surface adhesion. (Supplementary Figs. 5 and 6).
In the second set of tests, we investigated the influence of the
underlying surface roughness of the lubricated substrates on the Adhesion against human faeces. We further compared the adhe-
overall adhesion performance. The control surfaces in these tests sion characteristics of human faeces on LESS and other state-of-the-
included uncoated glass and silicone oil-infused SLIPS samples with art commercially available surfaces (Fig. 5a,b and Supplementary
either microscale (Ra= ~4 µm) or nanoscale roughness (Ra < 1 µm) Video 7). Specifically, we used glazed ceramic (a typical toilet mate-
on the underlying substrates (Supplementary Note 1). Our mea- rial), Teflon and silicone as the control surfaces. For these tests, we
surements showed that adhesion increased with increasing under- used a setup that allows human faeces samples to be released from
lying surface roughness (Supplementary Fig. 5 and Supplementary a drop rig at the same height onto an acrylic support where the test
Table 4). In general, the LESS-coated surface outperformed the con- coating is placed. When the support pin for the acrylic surface is
trol surfaces, including uncoated surfaces with or without lubrica- removed, the surface drops from a horizontal position to a vertical
tion, and SLIPS with different underlying roughnesses. According position, where the faeces are expected to slide down the face of the
to these tests (Fig. 4a), LESS coating can lead to 90% adhesion surface. In our tests, all of the commercial surfaces showed extreme
reduction in synthetic faeces (~40% solid content, with viscoelastic stickiness towards the human faeces samples. However, LESS-coated
characteristics similar to a type 3–4 healthy human faeces44,45) com- glass was the only surface showing non-stickiness towards the fae-
pared with uncoated surfaces. ces sample, and no noticeable residue was left behind (Fig. 5b).
Furthermore, we have shown in a different set of faeces impact tests
Water consumption of LESS. To investigate the volume of water that traces of faeces were left on a SLIPS-coated surface (with an
that would be required to clean LESS after contamination with the underlying surface roughness of ~1 µm) (Supplementary Fig. 8).
synthetic faeces, we built a simplified open-channel experimental Therefore, our tests further show that the LESS coating outperforms
setup to emulate the toilet-flushing process. Specifically, our setup various state-of-the-art surfaces when repelling human faeces.
is capable of generating a flow rate from 1 gallon min−1 (that is,
3.8 l min−1 with Reynolds number, Re = ~4,570, calculated based on Anti-bacterial performance of LESS. One important reason that
the hydraulic diameter46; Supplementary Note 6) to 2.5 gallons min−1 urinals or toilets need to be flushed and cleaned regularly is to
(that is, ~9.5 l min−1 with Re = ~11,600). The estimated wall shear prevent the growth of bacteria and the spread of infectious diseases
0.8
0.6
0.4
0.2
0
20 40 60
Solid content percentage (%)
b c
Flow rate Uncoated glass
Uncoated glass
4 (gallons min−1) 1.2 LESS-coated glass
LESS-coated glass
1.0
1.5 1.0
3 2.0
2.5
0.8
2
0.6
1 0.4
0.2
0
0
10 20 30 40 50 60 10 20 30 40 50 60
Solid content percentage (%) Solid content percentage (%)
Fig. 4 | Work of adhesion and water consumption characterizations. a, Work of debonding of synthetic faeces of varying solid contents on uncoated
bare glass and LESS-coated glass. Data were normalized to the work of debonding of the synthetic faeces on uncoated glass. b, Water consumption
measurements on uncoated and LESS-coated glass under different flow rates after being impacted by ~5 g of synthetic faeces with different solid content
percentages. Error bars represent standard deviations of four independent measurements. c, Cleaning water consumption performance of different
surfaces after synthetic faeces impact. The data were normalized to the cleaning water consumption on uncoated glass for each solid weight percentage of
synthetic faeces. All error bars represent standard deviations of four to six independent measurements.
and odour generation. In certain regions (for example, Brazil), rain- substrates can repel all bacteria-contaminated synthetic urine with
water is used as the source for toilet flushing. However, rainwater a sliding angle of a droplet (10 µl) of <5° (Supplementary Fig. 10).
can contain bacteria that may contaminate the sanitation facilities14. In cases where all lubricant is depleted, we have shown that it is
Owing to the presence of the mobile lubricant interface of LESS, much easier to sterilize LESS than other liquid-infused surfaces
we hypothesize that LESS may have a strong anti-biofouling perfor- with underlying surface roughness (Supplementary Fig. 11).
mance towards bacteria23,48,49. To verify this, we performed biofoul- In addition to rainwater and contaminated urine, we have also
ing analyses on LESS-coated substrates using natural rainwater and tested bacterial fouling on LESS-coated and untreated glass using
bacteria-contaminated synthetic urine. Specifically, we collected synthetic faecal waste of different solid content percentages (10,
rainwater from a house roof in State College, Pennsylvania and mea- 30 and 50%) spiked with 108 colony-forming units ml−1 E. coli
sured its bacteria content and concentration (Methods). We identi- (Supplementary Fig. 12). Following the procedures described in
fied the bacteria in the rainwater50 using a MALDI Biotyper system Supplementary Note 8, we counted the bacteria colony numbers on
(Fig. 5c, Supplementary Note 7 and Supplementary Table 12). We these substrates after 24 h of incubation. Specifically, no visible bac-
rinsed the LESS-coated substrate and uncoated bare glass with the teria colonies were found on the LESS-coated substrate while up to
collected rainwater for 1 min, then immediately incubated the sub- ~2.5 × 105 colonies m−2 of bacteria were observed on untreated glass
strates by attaching solid agar onto the surfaces in an incubator. (Fig. 5d and Supplementary Fig. 13).
After 36 h of incubation, we counted the bacterial colonies on these All of these results indicate that LESS has excellent anti-
surfaces. Specifically, no observable bacteria colonies were found biofouling performance and could therefore reduce the use of dis-
on all LESS-coated substrates, whereas the untreated glass surfaces infectants or other aggressive chemicals currently used for cleaning
were contaminated with the bacteria in the rainwater (Fig. 5c). and sterilization.
In a different scenario, 10 ml Escherichia coli-contaminated syn-
thetic urine was sprayed onto the test surfaces, followed by the afore- Durability of LESS. We have investigated the durability of the LESS
mentioned procedures for the biofouling characterizations. Our test coating against continuous shear flow, the impact of synthetic faeces
results are similar to those found in the rainwater tests, where all and mechanical abrasion. In the first test, we quantified the change of
LESS-coated samples showed no observable bacteria colonies while lubricant thickness by applying continuous shear flow with flow rates
the glass substrate showed significant contamination with bacteria at 1.0 and 2.5 gallons min−1, which correspond to shear stresses of
(Supplementary Fig. 9). We have further shown that LESS-coated ~0.1 and ~0.6 Pa, respectively (Fig. 6a and Supplementary Table 11).
a c
Dropping faeces
0.5 × 104
Shaft Surface holder Holding pin
0
b Glass LESS
d
3.5 × 105
10% solid faeces
1.0 × 105 2 µm
5
0.5 × 10
0
Glass LESS
Fig. 5 | Anti-fouling performance of LESS. a,b, Human faeces dropping test on commercially available surfaces and a LESS-coated surface. a, Schematic
showing the human faeces dropping test procedure: (1) faeces are dropped from a height of 75 mm; (2) faeces impact onto the test surfaces; and (3) the
surfaces are released from horizontal to vertical orientation to determine whether faeces will adhere onto the surface or not. b, Optical images showing
the test results for different surfaces. The human faeces adhered onto ceramic, Teflon and silicone, but slid off the LESS-coated glass. c,d, Anti-bacterial
performance comparison. c, Bacteria adhesion test with rainwater on glass (control) and LESS-coated glass. Inset: scanning electron microscope images
show two types of bacteria found in the rainwater sample. The dimensions of the inset optical image showing bacteria colonies are 10 mm by 10 mm.
d, Bacteria adhesion test with E. coli-spiked synthetic faeces (10, 30 and 50% solid content) on different surfaces. Inset: scanning electron microscope
image of E. coli. Error bars in c and d represent standard deviations of three independent measurements.
Under these flow conditions, we identified two regimes of lubri- of 0.5 kg onto sandpaper (grit size: P400) and slid the sandpaper
cant depletion depending on the initial lubricant thickness. In the against the LESS-coated sample (Methods). Our results showed that
first regime, when the lubricant thickness is >1 µm, the lubricant the LESS coating can withstand ~300 abrasion cycles before show-
depletion rate is relatively high, and is typically on the order of ing signs of degradation in liquid repellency performance (Fig. 6c).
~0.01 µm s−1. In the second regime, when the lubricant thickness We note that since the PDMS-grafted substrate of LESS is
is <1 µm, the lubricant depletion rate is significantly reduced to designed to adhere the silicone oil as opposed to aqueous liquids,
<0.01 µm s−1. Note that a typical dual flush toilet consumes either it is possible to replenish the lubricant layer by incorporating small
0.8 or 1.6 gallons flush−1, and each flush takes on the order of 5 s47. amounts of silicone oil in the flushing water so that the silicone
Based on our experimental measurements, we estimate that our oil can preferentially wet the surface through displacement wet-
LESS coating with an initial thickness of ~1 µm can sustain >500 ting (Fig. 6d and Supplementary Note 9). Experimentally, we have
flushes in typical toilet environments. shown that silicone oil wets the PDMS-grafted ceramic surface even
In the second test, we evaluated the lubricant durability using when the surface has been pre-wetted by water, and subse-
a water jet to simulate urination. It is known that the initial flow quently forms a functional layer to repel the water (Fig. 6d and
velocity of human urine ranges from 0.28–0.52 m s−1 (ref. 51). Based Supplementary Video 8).
on Bernoulli’s equation, we can estimate that the velocity of urine
impacting the surface is ~3 m s−1 (Methods and Supplementary Potential water-saving and environmental impacts. To further
Fig. 14). A water jet setup was built to achieve such an impact estimate the potential water saving of LESS coating on commer-
velocity. We designed each urination cycle to consist of a continu- cial toilets, we conducted a minimal flush water test on a 1.6 gal-
ous flow of liquid jet for ~20 s since it has been reported that all lons flush−1 (or 6 l flush−1) toilet to estimate the minimum water
mammals above 3 kg urinate for a constant time (~21 ± 13 s) regard- needed to flush the waste through the toilet trapway and drain line
less of their size52. Contact angle hysteresis and lubricant thickness (Supplementary Note 10 and Supplementary Fig. 17). In the test,
were measured after every five urination cycles. Our results showed we gradually reduced the water volume in the tank to flush the
that the LESS coating can withstand at least 50 urination cycles synthetic faeces until they could no longer be completely flushed
before further replenishment of the lubricant layer is necessary down the toilet. Our results showed that ~2.2 ± 0.1 l of flushing
(Supplementary Fig. 15). water are needed. This is equivalent to a potential water saving of up
Furthermore, we tested the durability of the LESS coating by to ~63 ± 2%. Using our experimental characterization results with
impacting synthetic faeces of various solid contents, and we found ~1 ml coating fluid to coat a toilet surface (~600 cm2), it is estimated
that the LESS coating can sustain ~10 to ~35 impact cycles (Fig. 6b that one could save up to >1,000 l of water for every ml of coat-
and Supplementary Fig. 16). The loss of durability of our coating ing fluid used for a typical 1.6 gallons flush−1 toilet. Furthermore,
was mainly due to lubricant loss caused by faeces adsorption at the we estimated the upper limit concentrations of the silicone oil in
point of contact. In addition, we characterized the robustness of our the flushed water to be on the order of ~0.03 parts per million
coating against mechanical abrasion. In our tests, we placed a mass (Supplementary Note 11). Recent studies have shown that silicone
Maximum number of
flush-to-clean cycles
2.5
6
20
4
2
10
0 10 20 30 40 50 60 10 20 30 40 50 60
Time (min) Solid content percentage (%)
0.5 kg
0.1 m s–1 d
LESS-coated glass Sandpaper
Droplet pinned Displacement wetting Droplet sliding
60
Phase 1 Phase 2 Phase 3
50
Sliding angle (°)
40
30
20
10
0
0 50 100 150 200 250 300 350 400
Abrasion cycle
Fig. 6 | Durability characterizations and lubricant replenishment of LESS-coated surfaces. a, Durability of the lubricant layer (silicone oil with a viscosity
of 20 cSt) under different shear flow conditions. The weight difference between LESS-coated and non-lubricated surfaces was measured and used to
estimate the lubricant thickness. b, Durability of the LESS coating under continuous faeces impact-and-flushing cycles. Error bars represent standard
deviations of three independent measurements. c, Abrasion characterization on LESS-coated glass. Phase 1 indicates that excess lubricant was removed
from the LESS-coated substrate. Phase 2 indicates that the thickness of the lubricant reached equilibrium with consistent liquid repellency performance for
up to ~300 abrasion cycles. Phase 3 indicates that gradual degradation of the coating and small particle accumulation from the sandpaper scratches began
to induce droplet pinning. Error bars represent standard deviations of three independent measurements. d, Schematic showing the displacement wetting
phenomenon on PDMS-grafted glass. Optical images show a facile lubricant replenishment process.
oil can be decomposed through various mechanisms in the envi- function53. The ability to prevent the fouling of faecal matter and
ronment38. More importantly, our LESS coating is not limited to bacteria will further reduce odour generation, which will make
grafted-PDMS and silicone oil systems, and can be formulated shared toilets more appealing to the public and could further pro-
using natural oils as the lubrication layer. mote safe and dignified sanitation. With an estimated >1 billion
toilets and urinals around the world13, it is anticipated that incorpo-
Summary rating LESS coating into sanitation systems worldwide could lead to
In summary, we have created a scalable, multifunctional LESS significant water saving and improved global sanitation, providing a
coating specifically designed to reduce adhesion to soft viscoelas- key technological solution to one of the United Nations’ Sustainable
tic solids (for example, human faeces) with applications aimed to Development Goals in clean water and sanitation.
minimize water consumption for sanitation and waste manage-
ment. We have shown that the LESS coating is capable of reduc- Methods
ing adhesion up to ~90% for soft viscoelastic solids, and requires Experimental details on the design and fabrication of the LESS coatings and
only ~10% of the cleaning water required for an untreated control preparation of synthetic faeces, as well as the experimental characterizations and
measurement procedures of the LESS coatings, are presented below.
surface. The significant adhesion and water consumption reduction
are due to the ability of the LESS coating to repel liquids, bacte-
LESS coating solution preparation. The LESS coating can be prepared by first
ria and viscoelastic solids with dynamic viscosities spanning over applying a PDMS-grafted layer onto a substrate, followed by the addition of a
nine orders of magnitude. Our LESS coating can be applied onto lubricant. Specifically, the PDMS-grafted layer was prepared by spraying a silane
various hydrophilic surfaces within minutes under ambient condi- solution onto a clean and dry hydrophilic substrate (for example, glass or ceramic)
tions through a spray-coating process. Furthermore, the excellent using a modified version of the process reported in ref. 26. The key ingredients
anti-biofouling property of LESS could minimize the use of aggres- of the silane solution comprise dimethyldimethoxysilane and a small amount of
sulfuric acid (Sigma–Aldrich). The silicone oil (with a viscosity of 20 cSt and the
sive chemicals currently used for sterilization, thus reducing envi- chemical formula (–Si(CH3)2O–)n) was used as the lubricant.
ronmental impacts. Our analysis indicates that it is possible to save
up to >1,000 l of flushing water for every ml of coating fluid used Synthetic faeces preparation. The recipe of synthetic human faeces was developed
for a standard 1.6 gallons flush−1 toilet. Our coating can also be from the original recipe developed at the University of KwaZulu-Natal in South
incorporated with novel waterless toilets to further enhance their Africa. The synthetic human faeces were composed of yeast, psyllium, peanut