**9. Future perspectives**

The boom in drug repurposing strategies may occupy the existing drugs from pharmacopoeia and the drug bank may get exhausted for further repurposing. Therefore, pharmaceutical companies with advanced biological and technological expertise should invest in biodiversity-oriented drug discovery programs to discover and develop early-stage new pharmacophoric compounds

*Trends in Molecular Aspects and Therapeutic Applications of Drug Repurposing for Infectious… DOI: http://dx.doi.org/10.5772/intechopen.100858*

#### **Table 1.**

*Directed repurposed drugs for infections [26–28].*

and fill their anti-infective pipelines while still taking the advantage of drug repurposing. Further, the advancement in nanotechnology may lead us to design better therapeutic formulations of repurposed drugs targeting pulmonary infections such as multidrug-resistant tuberculosis. Drug repurposing raises several concerns in terms of quality and ethical integrity of preclinical and clinical research specially during emergency pandemic situations such as COVID-19 involving accelerated drug approval based on statistical exploration of small, scientific data with the real-world population. This issue may not only increase the chances of adverse events; also, if the drug is withdrawn, the pharmaceutical industry may lose public confidence over healthcare needs. According to patent regulations, there are no safeguards for Intellectual property (IP) protection of drug development through the repositioning method. IP protection for repositioned drugs is limited. If the current evidence is not sufficient and does not meet the standards of according to regulatory guidelines, regulatory agencies such as the FDA or EMA, further preclinical and/or clinical studies may be necessary.


5. Conclusions

The conclusions of this research are as follows:

• The two lagoons have different dynamics.

Lagoons Reefs of Alacranes Reef and Chinchorro Bank: Ocean Reef of Mexican Atlantic DOI: http://dx.doi.org/10.5772/intechopen.88662

By virtue of its insular nature and the scarcity of freshwater, both reefs have remained safe from major alterations. Alacranes reef and Chinchorro Bank are a distant paradise that still have abundant fishing resources and diverse underwater life to marvel, as well as the possibility of discovering hidden secrets kept by the sea and time. However, we must consider and not forget that the overexploitation of resources can deplete the productivity of this place, which until now is one of the last places where coral reefs and memories of other times remain intact. The knowledge obtained from these systems must serve to conserve their natural resources, with special emphasis on endemic species, threatened, endangered, special protection, and those of current and potential economic importance, as well as preserving the reef landscape and its natural elements, for the enjoyment, recreation, exploitation, and elevation of the quality of life of social groups and visitors and for future generations. It should also encourage the conduct of research and studies that broaden and deepen this knowledge and contribute to the development of methods and alternatives for the sustainable use of resources.

The benchmarks of reefs in Mexico are changing, and they need to be redefined frequently to update them, in order for the management tools to be more effective and accurate; we hope that this contribution will go in that direction of conservation and maintenance of these magnificent ecosystems.


**Table 11.**

*Test results of LWACs with LC30 under water curing on different days.*

The compressive strength and elastic modulus of the specimens cured at 5°C meet the basic requirements (up to 90%) both with and without anti-freezing agent, but at 10°C, they can satisfy the requirements when added anti-freezing agent. Although the strength and elastic modulus of other groups fail the basic requirements, the hydration reaction does not stop but only diminishes. Compared with NWC, the strength of the specimen is higher, which shows that it helps promote the hydration reaction because of the heat preservation and inner curing effect of LWA. On the other hand, the strength of GLWC is slightly higher than that of ALWC under the same conditions. The reason is the same as the one mentioned above, namely, that the elastic modulus of gravel is larger than that of ceramsite.

**Type 200°C 300°C 400°C 500°C 600 °C** *ηT*

SLWC 32.05 28.98 25.01 21.35 17.22 56.4 GLWC 33.23 32.25 25.86 23.05 18.34 57.0 HALWC 32.65 31.82 25.14 22.21 17.90 56.8

SLWC 26.76 25.31 21.82 18.90 15.12 50.9 GLWC 29.77 26.96 23.19 19.14 15.95 50.9 HALWC 28.51 26.92 22.65 18.51 14.82 48.1

SLWC 2.22 1.93 1.59 1.36 1.14 46.2 GLWC 2.73 2.40 1.96 1.69 1.47 48.8 HALWC 2.53 2.25 1.80 1.55 1.35 48.0

SLWC 15.68 13.75 10.98 8.88 6.13 37.1 GLWC 16.89 16.46 14.53 11.19 8.76 50.8 HALWC 16.11 15.32 13.65 10.11 8.12 48.2

SLWC 1.3 4.6 5.6 6.7 7.2 GLWC 0.9 4.2 4.7 5.5 6.8 HALWC 0.8 4.2 4.9 5.8 6.9 *f*cu (MPa) ALWC 30.54 25.70 22.02 19.79 16.48 55.9

*f*c (MPa) ALWC 26.88 23.43 20.04 17.50 14.68 52.0

*f*ts (MPa) ALWC 2.06 1.79 1.46 1.25 1.07 46.1

*E*c (GPa) ALWC 12.61 10.13 8.19 6.62 5.03 34.5

*Notes: Δm stands for the ratio of mass after high-temperature treatment to that under room temperature. ηT*

Δ*m* (%) ALWC 1.1 4.5 5.4 6.4 7.0

*The Influence of Hybrid Aggregates on Different Types of Concrete*

*DOI: http://dx.doi.org/10.5772/intechopen.88254*

*c* **(%)**

*c stands for*

Also, fibre can enhance the strength and elastic modulus of specimens cured at negative temperature, and the laws are also the same; that is, the performance of

The uniaxial stress-strain curve of LWACs is similar to that of NWC, as shown in **Figure 3**, but the total strain of LWACs is significantly larger than that of NWC.

To summarise, the LWACs can meet the requirements of freezing process

concrete is better with elastic modulus of fibre increasing.

*the ratio of strength or elastic modulus at 600°C to that at room temperature.*

*Test results of LWACs for LC30 after elevated temperature treatment.*

**4.6 Uniaxial stress-strain curves of LWACs**

construction.

**91**

**Table 13.**

#### **Table 12.**

*Appearance characteristics of LWACs after high-temperature treatment.*

rises in temperature. On the other hand, the residual strengths of LWCAs after high-temperature treatment are very close to or even higher than that of NWC, which indicates that LWACs can be used for fire-resistant design. For example, the residual strength of axial compression is 95% at 200°C, 80–90% at 300°C, 70–75% at 400°C, 60–65% at 500°C, and around 50% at 600°C. The residual splitting tensile strength is around 90%, 75–80%, 60–65%, 5055%, and around 45% at 200, 300, 400, 500, and 600°C, respectively.

### **4.5 Properties of LWACs cured at negative temperature**

During the construction process used by the artificial freezing method, the ambient temperature in the working place is from 8 to 12°C in China. Concrete properties after curing at negative temperature are shown in **Tables 14** and **15**, where the specimen is wrapped with a layer of quilt after being poured and then put into a low-temperature test chamber.

*The Influence of Hybrid Aggregates on Different Types of Concrete DOI: http://dx.doi.org/10.5772/intechopen.88254*

*Notes: Δm stands for the ratio of mass after high-temperature treatment to that under room temperature. ηT c stands for the ratio of strength or elastic modulus at 600°C to that at room temperature.*

#### **Table 13.**

rises in temperature. On the other hand, the residual strengths of LWCAs after high-temperature treatment are very close to or even higher than that of NWC, which indicates that LWACs can be used for fire-resistant design. For example, the residual strength of axial compression is 95% at 200°C, 80–90% at 300°C, 70–75% at 400°C, 60–65% at 500°C, and around 50% at 600°C. The residual splitting tensile strength is around 90%, 75–80%, 60–65%, 5055%, and around 45% at 200, 300,

*T* **(°C) Colour Visible phenomenon** *w***max (mm)**

300 Light grey Fewer hairline cracks 0.06 0.04 0.05 0.04 400 Off-white More hairline cracks 0.16 0.12 0.14 0.12 500 Hazel Honeycomb cracks 0.20 0.20 0.20 0.18 600 Brownness Honeycomb cracks with surface wrapping 0.30 0.26 0.28 0.24

**Type 28 d 60 d 90 d 120 d 180 d** *ψ***c (%)**

SLWC 31.48 32.43 31.87 31.44 31.20 100.9 GLWC 34.43 35.18 35.09 34.92 34.81 102.8 HALWC 33.56 34.22 33.96 33.68 33.47 102.5

SLWC 30.87 31.56 30.78 30.49 30.15 100.6 GLWC 33.59 34.14 33.96 33.75 33.62 102.7 HALWC 31.35 32.84 32.61 32.39 32.18 102.9

SLWC 3.04 3.11 3.03 2.95 2.90 104.3 GLWC 3.15 3.23 3.20 3.18 3.15 104.3 HALWC 3.07 3.19 3.14 3.11 3.09 105.1

SLWC 21.62 22.24 22.85 23.41 23.98 115.3 GLWC 21.92 22.80 23.35 23.96 24.71 116.4 HALWC 21.58 22.45 23.09 23.62 24.35 116.3

*f*cu (MPa) ALWC 30.98 31.54 31.05 30.15 29.78 101.3

*f*c (MPa) ALWC 29.45 30.27 29.81 28.95 28.07 99.9

*f*ts (MPa) ALWC 2.96 3.03 2.95 2.86 2.79 104.5

*E*c (GPa) ALWC 21.23 21.74 22.35 23.24 23.79 115.2

**ALWC SLWC GLWC HALWC**

During the construction process used by the artificial freezing method, the ambient temperature in the working place is from 8 to 12°C in China. Concrete properties after curing at negative temperature are shown in **Tables 14** and **15**, where the specimen is wrapped with a layer of quilt after being poured and then put

400, 500, and 600°C, respectively.

*Notes: ψc stands for the softening coefficient of concrete.*

**Table 12.**

**90**

**Table 11.**

into a low-temperature test chamber.

**4.5 Properties of LWACs cured at negative temperature**

*Appearance characteristics of LWACs after high-temperature treatment.*

*Test results of LWACs with LC30 under water curing on different days.*

*Sandy Materials in Civil Engineering - Usage and Management*

*Test results of LWACs for LC30 after elevated temperature treatment.*

The compressive strength and elastic modulus of the specimens cured at 5°C meet the basic requirements (up to 90%) both with and without anti-freezing agent, but at 10°C, they can satisfy the requirements when added anti-freezing agent.

Although the strength and elastic modulus of other groups fail the basic requirements, the hydration reaction does not stop but only diminishes. Compared with NWC, the strength of the specimen is higher, which shows that it helps promote the hydration reaction because of the heat preservation and inner curing effect of LWA. On the other hand, the strength of GLWC is slightly higher than that of ALWC under the same conditions. The reason is the same as the one mentioned above, namely, that the elastic modulus of gravel is larger than that of ceramsite.

Also, fibre can enhance the strength and elastic modulus of specimens cured at negative temperature, and the laws are also the same; that is, the performance of concrete is better with elastic modulus of fibre increasing.

To summarise, the LWACs can meet the requirements of freezing process construction.

#### **4.6 Uniaxial stress-strain curves of LWACs**

The uniaxial stress-strain curve of LWACs is similar to that of NWC, as shown in **Figure 3**, but the total strain of LWACs is significantly larger than that of NWC.

*Notes: (1) wA stands for the ratio of anti-freezing agent to cement (by mass); (2) ηT c stands for the ratio of strength at 28 days and curing at negative temperature to that at room temperature; (3) the mixes are slightly different from Table 8.*

#### **Table 14.**

*Compressive strength of LWACs cured at negative temperature with anti-freezing agent for LC30.*

#### **Table 15.**

*Test results of LWACs cured at negative temperature without anti-freezing agent for LC30.*

The symbols of stress and strain obey the following rules: the plus sign '+' denotes tension; the minus sign '–' denotes compression.

Generally, the stress-strain curve can be expressed by Eqs. (3) and (4) [11]. Ascending curve:

$$y = a\mathbf{x} + (\mathbf{3} \cdot \mathbf{2}a)\mathbf{x}^2 + (a \cdot \mathbf{2})\mathbf{x}^3 \quad \mathbf{x} \le \mathbf{1} \tag{3}$$

Descending curve:

$$y = \frac{\varkappa}{\beta \left(\varkappa - 1\right)^2 + \varkappa} \quad \varkappa \ge 1 \tag{4}$$

Eqs. (3) and (4) can be fitted for all kinds of concretes, whether or not the curve is complete. In particular, direct measurement of the descending curve is not usu-

*α R***2** *β R***2**

Although **Figure 4** does not contain descending curves, the law of different LWACs is the same; that is, the ultimate stress decreases, and the ultimate strain increases with the temperature increase, which shows that the plastic deformation gets larger because the strength of the cement mortar matrix decreases. On the other hand, under the same temperature, the effects of a small quantity of NWA on the ultimate strain are not significant; only the effect on the ultimate stress is remarkable. At the same time, ALWC is similar to SLWC, and GLWC is similar to

**Strength grade Ascending curve Descending curve**

LC 30 0.3777 0.9332 4.7704 0.9921 LC 35 0.4398 0.9855 9.0217 0.9975

Under multiaxial compressive stresses, the ultimate compressive strength of concrete will increase significantly, and therefore the failure modes change. For example, ALWC undergoes the phenomenon of squeeze flow, and a plastic plateau

**Tables 17** and **18** show the bi- and triaxial ultimate compressive strengths tested by a large real triaxial test system, respectively. To reduce the friction, a two-layer polythene film with lithium base oil smeared between the layers is used, which can guarantee that the strength under single stress action (*σ*0) is close to the axial compressive strength (*f*c). In the test, *σ*0 is slightly smaller than *f*c, and the loading type is proportional loading. The samples were tested after 120 days of curing. The formulas for calculating bi- and triaxial ultimate strength are shown as

appears in the stress-strain curve under the two larger lateral stresses.

ally easy (**Figure 4**).

**4.7 Multiaxial strength of LWACs**

*Test curves of stress-strain under uniaxial compression for ALWC.*

*The Influence of Hybrid Aggregates on Different Types of Concrete*

*DOI: http://dx.doi.org/10.5772/intechopen.88254*

*Fitting coefficients and relative coefficients in Eqs. (3) and (4).*

Eqs. (5) and (6) [12], respectively:

HALWC.

**93**

**Figure 3.**

**Table 16.**

where *x* ¼ *ε ε*0 and *y* ¼ *σ σ*0 . *α* and *β* are fitting coefficients shown in **Table 16**. *ε*0 and *σ*0 stand for peak strain and peak stress under uniaxial compression, respectively.

*The Influence of Hybrid Aggregates on Different Types of Concrete DOI: http://dx.doi.org/10.5772/intechopen.88254*

#### **Figure 3.**

*Test curves of stress-strain under uniaxial compression for ALWC.*

#### **Table 16.**

*Fitting coefficients and relative coefficients in Eqs. (3) and (4).*

Eqs. (3) and (4) can be fitted for all kinds of concretes, whether or not the curve is complete. In particular, direct measurement of the descending curve is not usually easy (**Figure 4**).

Although **Figure 4** does not contain descending curves, the law of different LWACs is the same; that is, the ultimate stress decreases, and the ultimate strain increases with the temperature increase, which shows that the plastic deformation gets larger because the strength of the cement mortar matrix decreases. On the other hand, under the same temperature, the effects of a small quantity of NWA on the ultimate strain are not significant; only the effect on the ultimate stress is remarkable. At the same time, ALWC is similar to SLWC, and GLWC is similar to HALWC.

#### **4.7 Multiaxial strength of LWACs**

Under multiaxial compressive stresses, the ultimate compressive strength of concrete will increase significantly, and therefore the failure modes change. For example, ALWC undergoes the phenomenon of squeeze flow, and a plastic plateau appears in the stress-strain curve under the two larger lateral stresses. **Tables 17** and **18** show the bi- and triaxial ultimate compressive strengths tested by a large real triaxial test system, respectively. To reduce the friction, a two-layer polythene film with lithium base oil smeared between the layers is used, which can guarantee that the strength under single stress action (*σ*0) is close to the axial compressive strength (*f*c). In the test, *σ*0 is slightly smaller than *f*c, and the loading type is proportional loading. The samples were tested after 120 days of curing.

The formulas for calculating bi- and triaxial ultimate strength are shown as Eqs. (5) and (6) [12], respectively:

The symbols of stress and strain obey the following rules: the plus sign '+' denotes

Generally, the stress-strain curve can be expressed by Eqs. (3) and (4) [11].

*β*ð Þ *x* � 1 2 þ *x*

*ε*0 and *σ*0 stand for peak strain and peak stress under uniaxial compression,

*y* ¼ *x*

*Test results of LWACs cured at negative temperature without anti-freezing agent for LC30.*

*y* ¼ *αx* þ ð Þ 3‐2*α x*2 þ ð Þ *α*‐2 *x*3 *x*≤1 (3)

. *α* and *β* are fitting coefficients shown in **Table 16**.

*x*≥1 (4)

*c* **(%) GLWC,** *f***cu (MPa)** *ηT*

*c* **(%) GLWC,** *f***c (MPa)** *ηT*

**1 d 2 d 3 d 7 d 14 d 28 d 3 d 7 d 14 d 28 d**

2 6.2 12.5 17.9 27.3 — 32.1 98.7 ———— —

2 5.8 12.1 16.1 24.4 — 29.7 91.3 ———— —

3 5.3 11.8 15.4 18.9 — 27.5 84.6 ———— —

–5 0 4.9 11.3 16.5 20.5 24.7 29.3 90.1 16.9 21.1 26.0 31.3 90.9

�10 0 4.1 10.8 13.8 17.5 21.4 25.0 76.9 14.4 18.9 23.3 27.2 79.0

�15 0 37 8.5 10.3 13.3 15.8 18.6 57.2 11.4 14.3 17.5 20.7 60.1

*28 days and curing at negative temperature to that at room temperature; (3) the mixes are slightly different from*

**3 d 7d 14 d 28 d 3 d 7d 14 d 28 d** �5 14.46 18.41 22.36 24.63 83.0 15.81 20.34 24.64 26.45 85.0 �10 12.65 16.16 19.63 21.34 71.9 14.86 17.87 21.98 23.34 75.0 �15 10.88 13.18 15.54 16.62 56.0 11.94 14.49 17.21 18.15 58.3 *f*ts (MPa) *f*ts (MPa) –5 1.87 2.49 3.03 3.42 91.9 2.03 2.54 3.13 3.49 92.3 –10 1.69 2.15 2.71 2.99 80.4 1.83 2.30 2.75 3.06 81.0 –15 1.50 1.88 2.21 2.46 66.1 1.69 1.97 2.32 2.55 67.5 *E*c (GPa) *E*c (GPa) –5 9.43 13.22 16.49 18.77 92.0 10.02 14.23 17.56 19.36 94.0 –10 8.81 12.58 15.03 16.52 81.0 8.97 12.01 14.98 17.10 83.0 –15 8.26 11.57 13.61 14.28 70.0 8.44 11.15 13.22 15.04 73.0

*Compressive strength of LWACs cured at negative temperature with anti-freezing agent for LC30.*

*c* **(%)**

*c* **(%)**

*c stands for the ratio of strength at*

tension; the minus sign '–' denotes compression.

*T* **(°C)** *w***A (%) ALWC,** *f***cu (MPa)** *ηT*

*Sandy Materials in Civil Engineering - Usage and Management*

*Notes: (1) wA stands for the ratio of anti-freezing agent to cement (by mass); (2) ηT*

*T* **(°C) ALWC,** *f***c (MPa)** *ηT*

*ε*0 and *y* ¼ *σ*

*σ*0

Ascending curve:

*Table 8.*

**Table 14.**

**Table 15.**

Descending curve:

where *x* ¼ *ε*

respectively.

**92**

*Sandy Materials in Civil Engineering - Usage and Management*

$$
\sigma\_3 = \frac{1 + o\_2}{1 + o\_2^{\cdot 1}} \sigma\_2, o\_2 = \frac{\sigma\_3}{\sigma\_2} \tag{5}
$$

increasing lateral stress; the law is the same as for NWC, but the ratio of *σ*30 to *f*c is larger than that of NWC. Also, the stress-strain curves show that the deformation resistance capacity of LWACs is stronger than that of NWC, so the LWACs cannot be crushed easily and thus have higher strength under the action of multiaxial

*σ***3:***–σ***2:***–σ***1** *–σ***1 (MPa)** *–σ***2 (MPa)** *–σ***30 (MPa) Eq. (6) (MPa)** *E***r (%)** *σ***30 /***f***c**

*The Influence of Hybrid Aggregates on Different Types of Concrete*

*DOI: http://dx.doi.org/10.5772/intechopen.88254*

1:0.1:0.1 5.11 4.98 49.77 �51.1 2.6 1.56 1:0.25:0.25 19.58 19.10 75.85 �78.32 3.2 2.37 1:0.5:0.5 50.61 49.21 97.94 �101.22 3.3 3.06 1:1:0.1 6.48 60.81 60.51 �64 5.7 1.89 1:1:0.25 22.56 87.03 86.48 �90.24 4.3 2.70 1:1:0.5 55.61 107.37 106.78 �111.22 4.1 3.34 1:0.25:0.1 7.56 36.62 58.62 �60.60 3.3 1.83 1:0.5:0.1 19.04 30.98 72.85 �75.80 4.1 2.28 1:0.5:0.25 6.06 14.77 73.64 �76.16 3.4 2.30

**120 d**

The ultimate strength and elastic modulus of LWACs under traditional triaxial

All of the strength and elastic modulus values increase with increasing confining pressure. Under the same temperature and confining pressure, the effect on NWA is highest when using the lowest amount of hybrid aggregate, such as gravel, NS, and LWS. However, when the temperature is above 300°C, the strength of HALWC is smaller than those of SLWC and GLWC. At the same time, below 300 °C, the strength increases, except for HALWC, whose strength increases at temperatures below 200°C. The relationship between ultimate compressive strength and confining pressure can be expressed by Mohr-Coulomb theory as shown in Eq. (7).

*Triaxial compressive strength under proportional loading.*

$$\sigma\_3 = \frac{\sqrt{\sigma\_1 \sigma\_2 (1 + a\_1 + a\_3) \left(1 + a\_2 + a\_3^{-1}\right)}}{1 + a\_1^{-1} + a\_2^{-1}} \text{ or}\_1 = \frac{\sigma\_3}{\sigma\_1}, \alpha\_3 = \frac{\sigma\_2}{\sigma\_1} \tag{6}$$

The smaller relative error indicates that the test data are reliable and the formulas are correct. On the other hand, the multiaxial ultimate strength increases with

**Figure 4.**

*Test curves of stress-strain under uniaxial compression for LWACs after elevated temperature treatment. (a) ALWC, (b) SLWC, (c) GLWC, and (d) HALWC.*

#### **Table 17.**

*Biaxial compressive strength under proportional loading.*

## **Table 18.**

*σ*3 ¼ 1 þ *ω*2 1 þ *ω*‐1 2

ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi *σ*1*σ*2ð Þ 1 þ *ω*1 þ *ω*3 1 þ *ω*2 þ *ω*‐1

> 1 þ *ω*‐1 2

*Test curves of stress-strain under uniaxial compression for LWACs after elevated temperature treatment.*

*σ***3:***σ***2** *–σ***30 (MPa) Eq. (5) (MPa)** *E***r (%)** *σ***30** */ f***c**

1:0.25 40.94 �42.62 4.10 1.28 1:0.5 39.92 �41.75 4.58 1.24 1:0.75 39.88 �41.96 5.22 1.25 1:1 41.88 �44.28 5.73 1.31 *Notes: (1) σ30 stands for peak stress, namely, ultimate compressive strength. Er stands for relative error.*

*(a) ALWC, (b) SLWC, (c) GLWC, and (d) HALWC.*

*Biaxial compressive strength under proportional loading.*

The smaller relative error indicates that the test data are reliable and the formulas are correct. On the other hand, the multiaxial ultimate strength increases with

q � �

1 þ *ω*‐1

*Sandy Materials in Civil Engineering - Usage and Management*

*σ*3 ¼

**Figure 4.**

**Table 17.**

**94**

*σ*2*,ω*2 ¼ *σ*3

*σ*2

*ω*1 ¼ *σ*3 *σ*1

*,ω*3 ¼ *σ*2 *σ*1

3

(5)

(6)

**120 d**

*Triaxial compressive strength under proportional loading.*

increasing lateral stress; the law is the same as for NWC, but the ratio of *σ*30 to *f*c is larger than that of NWC. Also, the stress-strain curves show that the deformation resistance capacity of LWACs is stronger than that of NWC, so the LWACs cannot be crushed easily and thus have higher strength under the action of multiaxial stress.

The ultimate strength and elastic modulus of LWACs under traditional triaxial stresses are shown in **Table 19**.

All of the strength and elastic modulus values increase with increasing confining pressure. Under the same temperature and confining pressure, the effect on NWA is highest when using the lowest amount of hybrid aggregate, such as gravel, NS, and LWS. However, when the temperature is above 300°C, the strength of HALWC is smaller than those of SLWC and GLWC. At the same time, below 300 °C, the strength increases, except for HALWC, whose strength increases at temperatures below 200°C. The relationship between ultimate compressive strength and confining pressure can be expressed by Mohr-Coulomb theory as shown in Eq. (7).

cause the foamed concrete to crack. According to the properties, the bulk density of LWA is smaller than that of water, and thus the foamed concrete consists of LWA foamed by physical foaming, which can be called all-lightweight foamed concrete (ALWFC). It does not crack and also makes a higher-strength-grade concrete (up to LFC 30; LFC is the code name of strength grade of mortar). Because of these properties, it can be widely used in non-structure and structure concrete and pumped but not vibrated. The LWAs are SC and SP in foamed concrete in this

*) and test results of all-lightweight foamed concrete.*

Although there are countless air pores in ALWFC, most of these pores are discontinuous, so ALWFC has better durability. According to the test results, the carbonation depth generally does not exceed 5 mm in 56 days, and the resistance performance with regard to chloride ion permeability, that is, the electric flux after 6 hours, is smaller than 1000 C. On the other hand, the ALWFC also has better fire

Taking a reinforced ALWC beam, for example, the parameters of the tested

For the shear beam, because there is no warning before the occurrence of diagonal cracks, the diagonal cracks occur in the shear span section when the load is 20% of the ultimate load and then rapidly expand to the length of 100–150 mm. The initial width of the diagonal crack is generally 0.05 mm in the reinforced NWC beam compared to 0.03 mm in this study. At the same time, the maximum width of cracks and the deflection under service loads are 0.29 mm and 10.05 mm, respec-

The theoretical and test values of ultimate strength for normal and diagonal sections are shown in **Table 25**. All the test values slightly exceed the theoretical values. Compared to a reinforced NWC beam with the same stiffness, the width and height of the cross-section need to be increased by 18%, respectively. On the other

According to [16, 17], during the beam flexural test, the maximum crack width should not exceed 0.3 mm under service loads, and the deflection should not exceed *l*0/200 = 10.5 mm. The test values are 0.27 and 5.21 mm for the crack width and deflection, respectively, so ALWC can meet the code requirements. On the other hand, the crack load is about 28% of the ultimate load, and the service load is about

resistance, sound insulation, and sound absorption capabilities.

The test results according to GB50152-2012 [15] are as follows.

72%; these values are basically the same as those for the RC beam.

beams are shown in **Tables 21**–**25** and **Figures 5** and **6**.

study, and the mixes are shown in **Table 20**.

**Type** *m***C**

**Table 20.**

*Reference mixes (1 m3*

**(kg)**

*Notes: mF stands for the mass of foam agent.*

*m***FA (kg)**

*DOI: http://dx.doi.org/10.5772/intechopen.88254*

*m***SP (kg)**

*The Influence of Hybrid Aggregates on Different Types of Concrete*

*m***SC (kg)**

*m***W (kg)**

LFC 5 230 130 430 110 112 407 5.2 973 0.12 LFC 10 260 145 520 130 126 370 12.1 1185 0.26 LFC 20 360 198 543 136 173 280 24.5 1410 0.35 LFC 30 360 235 630 220 184 208 33.1 1723 0.42

*m***F (g)**

*f***cu28d (MPa)**

*ρ***d (kg/m3 )**

*λ* **(w/(m.k))**

**6. Properties of reinforced ALWC**

tively, thus meeting the code requirements.

**97**

#### **Table 19.**

*Test results of LWACs under traditional triaxial compression after elevated temperature treatment for LC30.*

$$\frac{\sigma\_{30}}{f\_{\text{c}}} = 1 + C \left(\frac{\sigma\_1}{f\_{\text{c}}}\right)^{\epsilon} \sigma\_1 = \sigma\_2 \tag{7}$$

where *C* and *c* are the fitting coefficients for each temperature group and concrete group, respectively.

The absolute values of relative error are all smaller than 5%.

### **5. Properties of lightweight sand foamed concrete**

In China, traditional foamed concrete generally consists of cement, NS, water, foam agent, and so on [13, 14]. Because the densities of cement and NS are significantly higher than the density of water, these particles sink easily and therefore

*The Influence of Hybrid Aggregates on Different Types of Concrete DOI: http://dx.doi.org/10.5772/intechopen.88254*

#### **Table 20.**

*Reference mixes (1 m3 ) and test results of all-lightweight foamed concrete.*

cause the foamed concrete to crack. According to the properties, the bulk density of LWA is smaller than that of water, and thus the foamed concrete consists of LWA foamed by physical foaming, which can be called all-lightweight foamed concrete (ALWFC). It does not crack and also makes a higher-strength-grade concrete (up to LFC 30; LFC is the code name of strength grade of mortar). Because of these properties, it can be widely used in non-structure and structure concrete and pumped but not vibrated. The LWAs are SC and SP in foamed concrete in this study, and the mixes are shown in **Table 20**.

Although there are countless air pores in ALWFC, most of these pores are discontinuous, so ALWFC has better durability. According to the test results, the carbonation depth generally does not exceed 5 mm in 56 days, and the resistance performance with regard to chloride ion permeability, that is, the electric flux after 6 hours, is smaller than 1000 C. On the other hand, the ALWFC also has better fire resistance, sound insulation, and sound absorption capabilities.


Furan Functionalized Polyesters and Polyurethanes for Thermally Reversible Reactive Hotmelt Adhesives

*Laxmisha M. Sridhar, Andrew T. Slark and James A. Wilson*

## **Abstract**

New reactive hotmelt (RHM) adhesives based on thermally reversible Diels-Alder networks comprising multifunctional furan and maleimide prepolymers are described. The prepolymer mixture is easy to apply in the bulk from the melt and after application to the substrates, the adhesive undergoes polymerization at room temperature resulting in crosslinked bonds. Due to their thermoplastic nature and low melt viscosity at hot melt application temperatures, the adhesives provide processing properties similar to moisture cured polyurethanes (PUR). The technology is isocyanate-free and does not require moisture to initiate the crosslinking. Bonding and tensile properties of the RHM adhesive can be readily tuned by prepolymer design and provide cure rates similar to PUR adhesives. The Diels-Alder adhesives provide versatile adhesion to a variety of substrates and good creep resistance up to the retro temperature. The adhesives show good thermal stability during application and can be recycled multiple times by simple heating/cooling of the bonds providing similar performance. Several furan and maleimide prepolymers were scaled up to multi-Kg quantities to demonstrate the potential for industrial scalability. The results demonstrate that furan-maleimide reversible chemistry can be used for RHM application as a more sustainable alternative to conventional moisture curing PURs which tend to contain harmful residual isocyanate monomers.

**Keywords:** Furan, maleimide, polyurethane, thermally reversible, recyclable, moisture-free, isocyanate-free, de-bonding

## **1. Introduction**

Several furan derivatives such as furfuryl alcohol, furfural and 5-hydroxymethylfurfural are bioderived. The industrial use of furan derivatives in polymeric applications is increasing - for example, furfuryl alcohol and furfural are used as raw materials to make furan resin, which is applied as a binder in polymeric concrete for construction [1]. 5-Hydroxymethylfurfural is a bioderived precursor for making 2,5-furandicarboxylic acid, which is a raw material used to make polyesters that are projected to replace phthalate plasticizers and even PET [2]. Other polymeric applications of furan derivatives include copolymerization in phenol-formaldehyde system [3], melamine-formaldehyde [4] and in biomedical applications [5]. In

addition, benzofuran type highly conjugated furan functional polyaromatics have been used in organic solar cells [6]. On an industrial scale, Furnova Polymers Ltd. sells several furan based polymeric materials for concrete, anticorrosion, composites and high temperature applications. Another potential application of furan derivatives is reversible crosslinking to generate polymers that can be used to bond substrates and which can be reworked or de-bonded by depolymerization at high temperatures caused by the retro Diels-Alder reaction. Incorporation of furanmaleimide based thermally reversible covalent crosslinks into polymers is known [7]. Upon heating above 80°C, the crosslinks dissociate and upon cooling the crosslinks reform. This property has been used in a number of applications such as in interpenetrating networks [8], remendability [9] and self-healing [10]. Adhesives are widely used to bond substrates in a number of consumer and industrial applications [11]. Crosslinked adhesives provide the highest bond strength and durability but have a negative environmental impact, since permanent adhesion prevents easy separation at their end-of-life which does not facilitate the re-use or recycling of materials. With increasingly stringent requirements for meeting fuel economy and recycling targets, the automotive and electronic industry has a strong need for debondable/reworkable adhesives that enable efficient repositioning in defective assemblies or end-of-life cycle recycling. Adhesives have also been used to replace metal fasteners to make the assembly lighter and thus help meet the fuel economy target. There have been several reports on the use of maleimide-furan Diels-Alder networks for reversible adhesives that include epoxy [12], polyacrylates [13] and polyurethanes [14]. However, in these reports, a low molecular weight monomeric maleimide compound such as *N*,*N*′-(4,4′-methylene diphenyl) bismaleimide (BMI), which is readily available commercially, was used. However, this BMI is highly toxic and unsuitable for practical consumer or industrial adhesive applications. It also has poor compatibility with most resin systems because of its rigid aromatic backbone and high polarity. While Diels-Alder based reversible non-isocyanate polyurethanes have been described before [14], little is known on their material properties. Most of the reported reversible polymeric systems based on furan-maleimide Diels-Alder networks required exposure to hot solvents for effective removal of components. In summary, the incorporation of Diels-Alder chemistry in a truly practical fashion has not yet been demonstrated.

Traditional hot melt adhesives based on, for example, polyolefins or polyamides are thermoplastic polymers which melt upon heating so that they can be applied to a substrate in a fluid state when hot. The cohesive strength of these adhesives is derived primarily from intermolecular physical forces which are formed upon cooling the adhesive. Polyurethane RHM adhesives are also applied in molten form and initial (green) strength is provided on cooling into a solid state. However, these adhesives are reactive (made from isocyanate functional prepolymers) which cure by moisture over time at ambient temperature resulting in adhesives with improved performance, such as adhesion strength, heat resistance, toughness and chemical resistance [15] when compared to thermoplastic hotmelts. The isocyanate prepolymers are typically made by reacting excess diisocyanates such as 4,4′-methylenebisphenyl diisocyanate (MDI) with polyols. Practical use of this chemistry (lower viscosity at hotmelt application temperature) requires that a NCO/OH ratio in the range 1.5 to 2.3 should be used for the synthesis of isocyanate prepolymers. The resulting compositions usually contain residual diisocyanates such as MDI, which are respiratory and skin sensitizers. Despite the successful development of moisture curable RHM, the technology has some limitations. For example, RHMs must be stored in the absence of moisture to prevent premature curing and require specialized application equipment for processing to keep moisture out. The cure rates of RHM's can also vary depending on atmospheric humidity level, moisture content

*Furan Functionalized Polyesters and Polyurethanes for Thermally Reversible Reactive Hotmelt… DOI: http://dx.doi.org/10.5772/intechopen.100426*

of the substrates, bond line thickness and moisture vapor transmission rate of the adhesive [16]. The compositions cure irreversibly and such adhesives cannot be used in applications where features such as repositionability, reworkability or recyclability are desired. There remains a need for improvement in RHM technology. Here we report on a new thermally reversible RHM that undergoes cross-linking at room temperature after application from the melt by copolymerization of polyfunctional furans and maleimides. Poly(ester urethane)-based prepolymers with maleimide end groups are developed and combined with the polyfunctional furans to provide thermally reversible polyurethane RHM's that are isocyanate-free and exhibit a range of physical properties similar to conventional polyurethane based RHMs. The new adhesives can be bonded, de-bonded and re-bonded multiple times without a significant change in performance.

## **2. Results and discussion**

### **2.1 Initial proof-of-concept, ambient curing and cured adhesive strength**

The thermally reversible RHM concept is schematically represented in **Figure 1** involving the dynamic equilibrium of Diels-Alder networks based on the combination of a polyfunctional furan crosslinker (indicated in blue color) and a maleimide prepolymer (indicated in red color). In the hotmelt state at higher temperatures (left hand side), network dissociation is favored - the Diels-Alder equilibrium is shifted toward free furan and maleimide functional prepolymers that provides the molten state. The fluid adhesive is then applied to substrates and after cooling, the prepolymers form crosslinked adhesive at ambient temperature via the [4 + 2] cycloaddition reaction between furan and maleimide functional groups (right hand side).

Reactive PUR hot melts are desirable due to their ease of application (involving low melt viscosity), high initial green (uncured) strength, curing at ambient temperature and versatile cured adhesion/durability. For initial investigations into the suitability of this concept, a variety of polyfunctional furans and maleimides were made in order to critically determine if they could behave like PUR hotmelts currently in use, i.e. (a) be applied as a fluid hotmelt at moderate temperatures, (b) crosslink at ambient temperature over a reasonable time period and (c) provide

#### **Figure 1.**

*Thermally reversible reactive hotmelt concept. For clarity, furan and maleimide functional reacting prepolymers are indicated in blue and red colors, respectively (see text for description).*

suitable cured bond strengths. To this end, a number of polyfunctional furans and maleimides were made, formulated into reactive hot melts and compared to a reference commercially available PUR adhesive. Polyfunctional furans F-1, F-2, F-3, F-4, F-5 & F-6 comprising ester and urethane linkages were made (**Figure 2**). F-2, F-3, F-4 and F-5 were made by simple addition of bio renewable furfuryl alcohol to the corresponding commercially available isocyanates. To mimic polyurethane like properties, F-6 possessing a PU backbone was made by initially reacting polyester or polyether polyols with MDI followed by bulk addition of furfuryl alcohol in the same pot. Trifunctional furan F-1 was synthesized by reacting 1,3,5-benzenetricarbonyl chloride with furfuryl alcohol in the presence of triethylamine as base in a solvent [17]. When the isocyanate starting material are liquids, a bulk process can be used to make the corresponding polyfunctional furans. For example, F-2, F-5 and F-6 were made in the bulk without the use of solvents simply by slow addition of furfuryl alcohol to the corresponding isocyanates. The polyfunctional isocyanate starting material used for F-3 synthesis is commercially supplied in 25% butyl acetate solvent and it was used as supplied. Several batches of polyfunctional furans were made at multi-Kg scale to demonstrate the industrial scalability of the process [18].

**Figure 2.** *Polyfunctional furan resins used in the study.*

*Furan Functionalized Polyesters and Polyurethanes for Thermally Reversible Reactive Hotmelt… DOI: http://dx.doi.org/10.5772/intechopen.100426*

### **Figure 3.** *Bismaleimide (BMI) resins used in the investigation.*

Several bismaleimide resins (BMI) were also investigated as components in the study (**Figure 3**). M-1 is a liquid BMI supplied by Henkel Corporation and it has a flexible 36-carbon dimer diol backbone (represented as C36). Two maleimide prepolymers M-2 & M-3, possessing poly(ester urethane) backbones were also used (discussed in detail in the later part of this chapter). Both the resins M-2 and M-3 were made in a bulk process by first reacting corresponding polyester polyols with excess MDI and subsequently capping the isocyanate terminated polyurethane prepolymers with 2-hydroxyethylmaleimide in a 2-step, one-pot process similar to the process used for the synthesis of F-6 [18]. The polyester polyols used for M-2 and M-3 (Dynacoll 7360 and 7231, respectively - obtained from Evonik) are used in typical moisture cured RHM formulations. Since excess diisocyanate is used in step 1 (1:2 stoichiometry of diol to diisocyanate used, some chain extension observed), a minor reaction product arising from the reaction of residual MDI remaining from step 1 with 2-hydroxyethylmaleimide was also observed. However, these adducts are nonvolatile as a consequence of their higher molecular weight and polarity (urethane & maleimide functionalities) as compared to MDI itself. Due to the presence of polyfunctional furans in the melt, they will be incorporated into the crosslinked Diels-Alder network. This is in stark contrast to conventional moisture cured RHM's based on isocyanate prepolymers, where the toxicity arises primarily from the volatility of residual MDI (at hotmelt application temperature) and potential hydrolysis to the corresponding aromatic amine. Prepolymers M-2 & M-3 possess semicrystalline and amorphous polyester backbones, respectively, and were used to investigate their impact on properties. A commercially available rigid aromatic bismaleimide M-4 (Daiwakasei industry) was also investigated as an additive in formulations to study its effect on properties. Several other polyfunctional maleimides were also made by simple addition of 2-hydroxyethylmaleimide to polyfunctional isocyanates by a process similar to that used for the synthesis of polyfunctional furans described in **Figure 2**. However, initial formulation work by blending these polyfunctional maleimides with furan prepolymers F-6 (possessing PU backbone) did not show much promise likely as a result of compatibility issues between highly polar polyfunctional maleimides and F-6. Hence, this approach was not pursued further.

Our initial formulation work focused on the feasibility of achieving room temperature cure and identifying structural features that contributed to bond strength at room temperature and 80°C. The components of formulas DA-1 to DA-7 shown in **Table 1** were mixed in the melt (typically at 120–150°C) until they became

*a Lap shear strength tested at ambient temperature [beechwood substrate, 25 × 25 mm bond overlap], unit MPa. b Lap shear strength tested at 80°C in air circulated oven [beechwood substrate, 25 × 25 mm bond overlap], unit MPa.*

*c A commercial isocyanate prepolymer from Henkel corporation was used as a reference.*

*n.d. means not determined.*

*The lap shear samples were tested using a JJ Lloyd tensiometer, with a load cell of 10 kN & a crosshead speed of 100 mm.min−1.*

#### **Table 1.**

*Diels-Alder formulations investigated in the study. The formulation components shown are in weight % (wt%).*

completely homogenous followed by coating on Beechwood substrate (250 μm coating thickness, see **Table 1**) and subsequent bonding.

The bonded substrates were allowed to cure at 23°C for 1 week at 50% relative humidity (RH) before testing for lap shear strength. As a control, a commercial isocyanate terminated polyurethane prepolymer (PUR) from Henkel Corporation was used. This control was bonded, cured at room temperature for 1 week and tested in the same way as the Diels-Alder based formulations.

Formula DA-1, which used a flexible BMI resin M-1 showed good curability at room temperature as evidenced by good lap shear strength development (DA-1 v PUR). Owing to the inherent thermal reversibility of the network, the lap shear strength at 80°C was slightly inferior to the control PUR. The addition of 10 wt% of rigid aromatic BMI M-4 improved the hot strength at 80°C (DA-6 vs. DA-1). However, the room temperature curability of DA-6 was negatively affected as evidenced by the lower lap shear strength. This is likely a result of a higher glass transition temperature (*T*g) of the network which would restrict mobility of the reactants at room temperature. By partially substituting F-1 with flexible bifunctional F-5 (maintaining crosslinks in the network), the room temperature curability was improved at the expense of 80°C strength (DA-7 v DA-6). Similar observations were made with formulas DA-2 and DA-3. Use of flexible furan F-2 in DA-2 gave good lap shear strength at room temperature. In contrast, rigid furan F-3 used in formula DA-3 improved the hot lap shear strength at the expense of room temperature strength. Formula DA-5 that contains F-4 with a rigid aromatic backbone showed lap shear performance similar to DA-3 at both room temperature and 80°C. For comparison, a linear Diels-Alder network (DA-8 formula) was made by blending bifunctional precursors F-5 and M-1 and allowing to copolymerize at room temperature for 3 days. A size exclusion chromatography (SEC) molecular weight comparison of this polymer with M-1 and F-5 showed a several-fold increase in molecular weight arising from step-growth polymerization at room temperature (**Figure 4**). In addition, there were very low levels of reactants M-1 & F-5 present. While both M-1 and F-5 are medium viscosity liquids at ambient temperature (2,000–5,000 cP), the linear polymer was a gel like material at room temperature

*Furan Functionalized Polyesters and Polyurethanes for Thermally Reversible Reactive Hotmelt… DOI: http://dx.doi.org/10.5772/intechopen.100426*

#### **Figure 4.**

*SEC chromatogram comparison for M-1 (Mp = 1298 Da), F-5 (Mp = 1116 Da) and the corresponding linear Diels-Alder polymer DA-8 (Mp = 15294 Da). Mp refers to peak molecular weight. The chromatograms were run using Waters e2695 instrument comprising three Agilent Polypore 7.8\*300 mm GPC columns using THF as mobile phase and Waters 2414 as a RI detector against polystyrene standards.*

and a liquid at 60°C as a likely consequence of low *T*g (both M-1 and F-5 possess flexible backbones). No lap shear measurements were performed on this system. The molecular weight for the polymer is likely to increase further if left at room temperature for a longer time period since it would take about a week for high prepolymer conversion (discussed later in the chapter). The SEC data presented here further demonstrates the room temperature reactivity of the Diels-Alder based systems.

The cause of contrasting lap shear results obtained with formulations DA-2 and DA-3, which contain the same maleimide component M-1 but structurally different furans F-2 and F-3, respectively, was investigated by differential scanning calorimetry (DSC) studies. It should be noted that F-2 contains a flexible backbone while F-3 possesses a highly rigid cycloaliphatic backbone. **Figure 5** shows DSC thermograms for neat F-2 and F-3, and the corresponding formulas DA-2 and DA-3, respectively. Polyfunctional furan F-2 appears to be completely compatible in the DA-2 formulation with only a *T*g at 10°C for the crosslinked network and

#### **Figure 5.**

*DSC thermograms (TA instruments Discovery DSC 25) of F-2, DA-2, F-3 and DA-3. Reproduced from [17] with permission from Royal Society of Chemistry.*

an endotherm above 100°C corresponding to the retro Diels-Alder depolymerization. No residual melting point for F-2 was recorded. In contrast, the cured DA-3 network shows a residual melting point at 76.7° C for F-3 along with the expected endotherm for the depolymerization. This indicates that the rigid F-3 is partially incompatible at room temperature in DA-3, which could explain the lower lap shear strength obtained at room temperature (DA-3, **Table 1**). The partial incompatibility could also be resulting from the higher concentration of F-3 (higher molecular weight) required in DA-3 (as compared to DA-2) for 1:1 molar equivalence between furan and maleimide functionalities. The higher *T*g of the partially cured network is also likely contributing to incomplete polymerization at room temperature. The DA-3 formula likely needs to be heated to above the melting point of F-3 for better compatibility, which is reflected in higher lap shear strength observed at 80°C. A similar effect may be operating in DA-5, which uses rigid furan F-4, although this was not investigated in detail.

Since the Diels-Alder network formation does not require moisture for curing, in principle the cure rate is independent of moisture availability. **Figure 6** shows comparison of cured films of DA-1 and the moisture cured PUR control. The DA-1 cured film appears clean without bubbles (**Figure 6**, left image). In contrast, the moisture curing PUR control shows significant bubble generation arising from CO2 evolution during moisture cure (right image). If CO2 cannot diffuse out of the bond line during application, the pressure generated can cause substrate deformation, especially when non-porous substrates are bonded together, such as plastics and metals.

Overall, these preliminary results indicate that a combination of both soft and rigid backbones are required in the prepolymers to obtain a balance of adhesion strength at room temperature and 80°C. The effect of *T*g of the crosslinked network on prepolymer conversion at room temperature is discussed in detail at a later section. Formula DA-4, which used the rigid F-3 crosslinker and two bismaleimides M-2 and M-3 possessing poly(ester urethane) backbones showed lap shear performance very similar to the PUR control. This initial investigation showed that the new thermally reversible RHM could be applied as fluid hotmelts at moderate temperatures, would cure at similar rates to conventional PUR at ambient temperature and that similar bond strengths could be achieved. Based on these initial results, DA-1 and DA-4 were selected for more detailed investigations.

**Figure 6.** *Appearance of cured films of DA-1 (left) and moisture cured PUR control (right).*

*Furan Functionalized Polyesters and Polyurethanes for Thermally Reversible Reactive Hotmelt… DOI: http://dx.doi.org/10.5772/intechopen.100426*

#### **Figure 7.**

*Melt viscosity of DA-4 at different application temperatures as a function of time (run using Brookfield Viscometer model RVDV-1 with a Model 74R temperature controller and Thermosel unit using spindle no. 27). Reproduced from [17] with permission from Royal Society of Chemistry.*

### **2.2 Thermal stability**

In real world applications, RHM adhesives are held at the desired application temperature (e.g. in the range 120–150°C) for a number of hours until all the substrates are coated and bonded in the production line. This requires good thermal stability up to several hours in the open air. To investigate the stability of the Diels-Alder RHM system, DA-4 (which is compositionally closest to PUR) was held at a specified melt temperature and the viscosity was measured as a function of time using a Brookfield viscometer (**Figure 7**). The initial melt viscosity is in the range 7,000–17,000 mPa.s at 135°C and 150°C, similar to the melt viscosity of PUR products which provide good substrate wetting. The DA-4 formula also shows good thermal stability at 135°C and 150°C up to about 6 hours. It should be noted that the viscosity profile of the DA-4 at these temperatures is very similar to the moisture cure PUR benchmark. To test the limit of thermal stability, DA-4 was also held at 180°C for several hours. However, significant viscosity increase was observed likely arising from homopolymerization of the free maleimide component. It should be noted that this is not a typical temperature used for reactive hotmelts in current industrial applications since the NCO prepolymers would be highly unstable at these temperatures as trimerization of isocyanate functionality is possible.

### **2.3 Green (initial) strength**

An important processing property requirement of RHM adhesives is green strength, which is the initial bond strength soon after the adhesive is applied from the melt and before moisture curing takes place. Liquid NCO prepolymers applied at ambient temperature have very little green strength as there is little cohesion to keep substrates apart, and substrates need to be clamped together before sufficient strength is built up. However, reactive PUR hot melts have the advantage that the green strength is relatively high and additional steps are not required to hold substrates together before curing takes place. This results from non-covalent interactions providing physical strength on cooling, provided by hydrogen bonding and crystallization. DA-1 and DA-6 (similar formulas but DA-6 with 10% additive) were

#### **Figure 8.**

*Green strength development comparison of DA-1 (red), DA-6 (green) with PUR control (blue). Test performed on ARES-M rheometer (TA instruments) using dynamic oscillatory test method in which 10 rad/s oscillating frequency was used with 1% strain and the data recorded at 11 second intervals.*

evaluated for green strength in comparison to the PUR reference by rheological analysis. Experiments were performed with rapid cooling where adhesive compositions were positioned between parallel plates cooled from application temperature to 40°C at a cooling rate of 60°C per minute in nitrogen atmosphere, and then held for 20 minutes to evaluate the storage modulus (elastic component) as a function of time. **Figure 8** shows that DA-1 (comprising a very flexible aliphatic backbone) has a lower modulus than the PUR reference. However, this can be tuned since DA-6 (similar to DA-1 but with 10% additive) provides higher green strength than the reference as a consequence of the incorporation of a rigid, aromatic backbone. These results indicate that the green strength of Diels-Alder based RHM systems can be tuned by the appropriate choice of prepolymer composition.

### **2.4 Cure dynamics and adhesion development**

FT IR spectroscopy was used to investigate the ambient temperature conversion of the DA-1 composition after deposition from the melt by monitoring the characteristic maleimide absorption at 696 cm−1 (**Figure 9**). In the cured film (top IR trace indicated in black color), the 696 cm−1 band is not visible. After heating the film at 150°C for 1 h and immediately cooling, this band is prominent initially but decreases in intensity as the crosslinking progresses. The decrease is rapid in the first two days after deposition followed by a slower change in the next several days. The band is barely visible after 10 days of storage at room temperature.

In a separate experiment, the composition DA-1 was applied from the bulk between two Beechwood substrates (25 × 25 mm bond overlap) and bond strength development was compared over time at room temperature and at 60°C (**Figure 10**). At room temperature, the bond strength increases substantially over a period of 48 hours before tending to a plateau. This is consistent with the decrease of the maleimide absorption peak at 696 cm−1 as Diels-Alder cycloaddition progresses as shown in **Figure 9**. It is interesting to note that substrate failure begins to occur at a bond strength of about 4 MPa and that this is reached in approximately 24 hours at room temperature. In comparison, the strength development at 60°C is more rapid and reaches 4 MPa in approximately 2 hours.

*Furan Functionalized Polyesters and Polyurethanes for Thermally Reversible Reactive Hotmelt… DOI: http://dx.doi.org/10.5772/intechopen.100426*

#### **Figure 9.**

*IR spectra of DA-1 cured network over the range 600–1000 cm−1 before heating (top) and over time at ambient temperature after deposition from the melt. IR measurements were recorded using a PerkinElmer FT-Infra-red spectrometer equipped with a UATR Two accessory. Reproduced from [17] with permission from Royal Society of Chemistry.*

#### **Figure 10.**

*Comparison of lap shear strength development on Beechwood substrate for DA-1 formulation at room temperature (RT) and 60°C as a function of time.*

### **2.5 Cured properties and adhesion**

For isocyanate terminated PUR moisture cure adhesives, the mechanical performance is determined by a combination of covalent crosslinking formed by moisture curing (including urea formation), H-bonding of urethane groups and crystallinity from polyester segments present in the prepolymer backbone. The urethane and urea groups contribute to the flexibility & elongation of the cured network while the crystallinity of the polyester segment causes further reinforcement of modulus and stiffness. The results discussed previously demonstrated that the lap shear strength, room temperature curability and mechanical properties can be tuned by proper choice of polyfunctional furans possessing rigid or flexible backbones. However, to achieve properties similar to moisture cured PUR, the use of polyurethane backbones with reinforcing crystalline segments is necessary. We sought to achieve this initially by making furan functional PU prepolymers F-6 possessing semicrystalline polyester segments and blending them with polyfunctional maleimides obtained by the addition of 2-hydroxyethylmaleimide with polyfunctional isocyanates. However, our initial results did not show promise likely as a

result of compatibility issues. As an alternative approach, maleimide terminated PU prepolymers M-2 & M-3 possessing poly(ester urethane) backbones were made (**Figure 3**) in a one-pot bulk process and formulated with polyfunctional furans. The synthetic process is very similar to that utilized for the synthesis of isocyanate terminated PUR prepolymers except that an additional solvent-free process was used to react the terminal isocyanate groups with 2-hydroxyethylmaleimide in the same-pot [18]. The prepolymers were scaled up to several Kgs with reproducible performance (discussed in the next section) to demonstrate the industrial scalability of the process. A blend of M-2 comprising a semi-crystalline backbone and M-3 with amorphous polyester segment was used to achieve a balance of room temperature and 80°C lap shear strength. Such combinations of semi-crystalline and amorphous polyester polyol segments are also used in moisture cured PUR products to provide the necessary balance of properties suitable for applications.

The DSC thermogram for the cured DA-4 network shows a *T*g of −11.7°C and a melting point (*T*m) at 50°C for the semi-crystalline polyester segment present in copolymerized prepolymer M-2 (also seen in the DSC thermogram of M-2). In addition, there is an endotherm at 140.4°C resulting from the retro Diels-Alder depolymerization (**Figure 11**). We have previously shown that the position of this endotherm is a function of the heating rate, with much lower temperatures obtained at 1°C per minute compared to 10°C per minute [17]. Compared to DA-4, the thermograms for DA-2 and DA-1 do not exhibit a melting point due to the amorphous backbones but have higher *T*g values of 10°C and 47.3°C, respectively. In addition, the peak position and magnitude of the endotherms due to the retro Diels-Alder reactions are relatively low for DA-4 compared to the DA-1 and DA-2. This is due to the relatively lower crosslink density in DA-4 arising from lower concentration of furan and maleimide functional groups since the molecular weights of M-2 and M-3 are much higher compared to M-1 used in DA-1 and DA-2. A similar phenomenon has been observed in self-healing coatings [19]. It is important to note that no residual melting point for F-3 was seen in DA-4, which indicates good compatibility in the formula (compared to DA-3, **Figure 5**).

The conversion in the Diels-Alder polymerization of DA-1, DA-2 and DA-4 formulas was investigated after deposition from the melt by monitoring the characteristic absorption at 696 cm−1 for the maleimide functionality. **Figure 12** shows the relative intensities of this band as a function of time. The initial absorption

#### **Figure 11.**

*DSC thermogram for DA-4 and comparison with M-2, DA-1 and DA-2 (TA instruments Discovery DSC 25). Reproduced from [17] with permission from Royal Society of Chemistry.*

*Furan Functionalized Polyesters and Polyurethanes for Thermally Reversible Reactive Hotmelt… DOI: http://dx.doi.org/10.5772/intechopen.100426*

#### **Figure 12.**

*IR absorbance comparison of maleimide absorption at 696 cm−1 as a function of time for DA-1, DA-2 and DA-4. Absorbance values after 7 days are: 0.027 for DA-1 (82% conversion), 0.014 for DA-2 (88% conversion) and 0.003 for DA-4 (95% conversion). Reproduced from [17] with permission from Royal Society of Chemistry.*

intensities correspond well to the relative concentration of the maleimide functionality in the 3 formulas (DA-1 > DA-2 > DA-4). In spite of the significant difference in reactive functional group density, prepolymer molecular weight and backbone, all the three formulas showed a similar reactivity tendency in the first 48 hours. There was fast reduction in the first 48 hours, followed by slower decrease, before reaching a plateau at 7 days. A closer look at the relative absorption after 7 days however showed some difference in conversion. DA-4 with the lowest *T*g (−11.7°C) shows the highest conversion (95%) while DA-1 with the highest *T*g shows the lowest conversion (82%). This result is consistent with higher mobility typically seen in lower *T*g networks. The lower room temperature lap shear strength previously observed with compositions DA-3, DA-5 and DA-6, which used polyfunctional furans with rigid backbones, are also likely to result from lower conversion due to restricted mobility (**Table 1**). These formulas showed better 80°C lap shear strength than the PUR reference.

The bond strengths of DA-1 & DA-4 were compared to the control PUR system on three different types of material substrates – wood, plastic and metal (**Figure 13**). For bonding Beechwood substrates at ambient temperature, the lap shear strengths of both Diels-Alder networks were similar to the reference PUR. However, at 80°C the bonding performance was slightly better for the irreversible PUR system (**Figure 13A**). The bond strength of DA-4 on polycarbonate (PC) was slightly superior to the reference PUR at ambient temperature (**Figure 13B**). On aluminum substrate in particular, the bond strength was exceptional for the Diels-Alder formula. These results demonstrate the versatile adhesion performance of the Diels-Alder based networks using different substrates and surface chemistry.

### **2.6 Cured mechanical properties**

The mechanical properties of thermally reversible DA-1 and DA-4 were compared to the moisture cured PUR benchmark. As a result of higher crosslink density obtained from low molecular weight prepolymers, DA-1 exhibits the highest break stress and lowest elongation (**Table 2**). Due to the higher molecular weight backbones used in M-2 and M-3 prepolymers, DA-4 has a lower crosslink density. This results in stress–strain and elongation properties similar to PUR benchmark.

#### **Figure 13.**

*(A) Lap shear strength comparison of DA-1, DA-4 and control PUR at ambient temperature and 80°C using Beechwood substrate. (B) Bond strength comparison of DA-4 and control PUR using different substrates at ambient temperature. Reproduced from [17] with permission from Royal Society of Chemistry.*

*b Determined by vertical creep measurements (25 × 25 mm bond overlap, 1 Kg static load.*

#### **Table 2.**

*Mechanical properties of films and creep resistance measurements for DA-1 and DA-4 compared to PUR control.*

It should be noted that DA-4 and the reference PUR both comprise semi-crystalline polyester segments at a similar overall concentration.

The mechanical properties of DA-1, DA-2 and DA-4 Diels-Alder networks were evaluated by DMTA using 250 μm cured films (**Figure 14**). The 3 networks have high stiffness below their respective *T*g. DA-4 has the highest mechanical properties due to the presence of the semi-crystalline segments resulting from M-2 and the modulus changes significantly above ambient temperature as a consequence of melting (**Figure 14A**). Above the *T*g and *T*m (for DA-4), the change in modulus is slow for the 3 networks in the temperature range 40–80°C. There is then rapid

#### **Figure 14.**

*(A) Storage modulus vs. temperature of DA-1, DA-2 and DA-4. (B) Tanδ vs. temperature of DA-1, DA-2 and DA-4 from DMTA on 250* μ*m films. Reproduced from [17] with permission from Royal Society of Chemistry.*

## *Furan Functionalized Polyesters and Polyurethanes for Thermally Reversible Reactive Hotmelt… DOI: http://dx.doi.org/10.5772/intechopen.100426*

decrease in modulus at higher temperature (above 80°C) with the tan *δ* reaching 1 (**Figure 14B**), at which point there is a transition from a solid to a liquid phase. This is the temperature range where the Diels-Alder equilibrium shifts predominately to the prepolymeric dissociated state resulting in stretching and failure of the film samples being tested.

Comparison of crosslink densities of the Diels-Alder networks shows a correlation between crosslink density and the rapid decrease in storage modulus (*G*') above 80°C. DA-1 has a higher functional group concentration because of lower molecular weight reactants (1.63 mol.Kg−1, calculated based on stoichiometry of reagents), which results in higher crosslink density. Even though the Diels-Alder equilibrium starts to shift to the prepolymeric state above 80°C, the higher crosslink density present in DA-1 delays the rapid decrease in *G*' to approximately 97°C. In contrast, DA-4 comprising a lower crosslink density (lower functional group concentration of 0.39 mol.Kg−1) shows a rapid change in modulus at approximately 85°C.

A further important property of RHM adhesives is their creep behavior at higher temperature under static load. The creep resistance of reversible DA-1 and DA-4 was compared with the irreversible moisture cure PUR control up to 110°C (**Table 2**). This upper temperature limit was chosen based on tan *δ* data, which shows liquidlike behavior for DA-1 & DA-4 networks (**Figure 14**). Creep experiments were performed on bonded joints under a static load of 1 Kg in an oven held at a particular temperature for 24 h. The creep resistance of the reversible Diels-Alder system correlates well with the crosslink density of the cured network. The DA-1 system with a higher crosslink density was resistant to creep at 80°C but the joints failed at 90°C. The DA-4 system which has a lower crosslink density failed at 80°C but was resilient to creep at 70°C. The irreversible PUR control was creep resistant over the entire temperature range. Both the Diels-Alder networks were creep resistant in a temperature range well above their *T*g and *T*m (for DA-4). This result indicates a significant advantage of these reversible Diels-Alder based networks as compared to some of the reported creep behavior of other covalently adaptable networks [20]. The failure temperature observed in the creep experiment of DA-1 and DA-4 networks correlates well with their respective DMTA data, which indicates significant change in stiffness close to the failure temperature (**Figure 14**). Since the data shows strong dependency of creep resistance on crosslink density, it is feasible to develop new Diels-Alder systems with improved performance by changing the architecture of the furan and maleimide components.

## **2.7 Reversibility and recyclability**

For a truly sustainable adhesive, its material properties and adhesion should not change significantly after multiple reprocessing and re-use cycles. In several industrial applications (including assembly of components in the automotive industry) the bonded substrates need to be repositioned if a defect is found or recycled at the end of their life. This requires that the adhesive shows similar performance when subjected to multiple bond, de-bond, re-bond cycles. The repeatability of lap shear adhesion of DA-1 and DA-4 formulas over multiple cycles was tested using adhesive films cured between aluminum joints. Initial bonds were formed using a film adhesive that was heated to the hotmelt dissociated state to wet the substrates and then cured for 7 days at ambient temperature before bond strength measurement. For the 2nd, 3rd and 4th re-use, the same joints were broken after the lap shear test and reassembled using the residual adhesive on the surface by heating and re-bonding of the broken joints. The adhesion data over multiple cycles is shown in **Figure 15**. Both DA-1 and DA-4 are relatively robust in performance after multiple bond, de-bond,

### **Figure 15.**

*Bond strengths of DA-1 and DA-4 over several cycles of bonding, de-bonding and re-bonding using the same aluminum substrate. Reproduced from [17] with permission from Royal Society of Chemistry.*

re-bond cycles. The bond strength of the DA-1 system is unchanged after 4 re-use cycles while DA-4 shows a small decrease in strength (**Figure 15**). This is a significant result despite the likelihood that some adhesive could be lost or migrate out of the bond line during multiple heating, re-bonding and lap shear testing.

## **2.8 Development of the concept to soft cured Diels-Alder networks**

As an extension of the RHM study, an initial investigation was performed on Diels-Alder based systems that give cured networks with a lower modulus at ambient temperature, approaching the pressure sensitive adhesive (PSA) region (104 to 105 Pa). This study required the synthesis of higher molecular weight maleimide prepolymer M-5 comprising an amorphous polyester segment with a lower *T*g. To this end, M-5, containing Dynacol 7250 backbone (molecular weight 5500 g. mol−1 and *T*<sup>g</sup> − 50°C as compared to 3500 g.mol−1 and *T*<sup>g</sup> − 30°C for Dynacol 7231 used previously), was made using a process similar to that used for M-3 synthesis (**Figure 16**) [18]. An additional furan F-7 possessing a very soft backbone was also made by simple addition of furfuryl alcohol to Desmodur XP2599 (Covestro). The structure of this commercially available isocyanate (functionality >3) is not known and the stoichiometry for the synthesis of F-7 was calculated based on isocyanate equivalent weight.

**Figure 16.** *Prepolymers used for the development of soft Diels-Alder cured networks.* *Furan Functionalized Polyesters and Polyurethanes for Thermally Reversible Reactive Hotmelt… DOI: http://dx.doi.org/10.5772/intechopen.100426*

**Table 3.**

*Diels-Alder formulas used for the development of soft cured networks. The formulation components shown are in weight %.*

#### **Figure 17.**

*Melt viscosity stability of DA-9 and DA-10 formulas as a function of time at 135°C.*

The cured network DA-9 comprising F-2 and M-5 showed high elongation and a low modulus. DA-10 comprising F-7 and M-5 showed even lower modulus and similar elongation properties (**Table 3**). **Figure 17** shows that melt viscosity remains relatively low for these types of formulation and that thermal stability is good over several hours at 135°C. While these amorphous networks with relatively low crosslink density are not expected to have the same level of creep resistance as the networks DA-1 and DA-4 required for RHM applications, they may be sufficient for PSAs. In conventional solvent borne PSA technology, permanent crosslinking is typically achieved by the use of low level of metal chelates, which upon evaporation of the solvent bind with pendant hydroxyl or carboxylic functionality from the polymer backbone and provide crosslinks [21]. The degree of crosslinking is controlled by the amount of metal chelate used in the formulations. The crosslinking mediated by the Diels-Alder reaction could potentially be an effective metalfree substitute for new PSA development especially as a hotmelt PSA. In hotmelt PSA's, the adhesive is applied from the melt to substrates (no solvent used unlike solvent borne PSA and environmentally friendly) and the adhesive after application to substrates requires a crosslinking mechanism (such as UV induced crosslinking) for sufficient shear adhesion strength. Since the depolymerization gives the melt state (and sufficiently low viscosity to wet the substrates), the Diels-Alder mediated room temperature crosslinking could be an effective alternative method to achieve crosslinking in hotmelt PSAs. More formulation work (for example with tackifiers) is needed to develop formulations that would meet the tack, peel and shear adhesion requirements.

## **3. Conclusions**

Polyester and polyurethane functional furans were reversibly copolymerized in the bulk with multifunctional maleimide prepolymers in a successful demonstration of a thermally reversible reactive hotmelt (RHM) adhesive concept that is

isocyanate-free. At the hotmelt temperature, the adhesive remained in the prepolymeric dissociated state with a low melt viscosity, enabling facile application to substrates and bond formation. Upon cooling, ambient temperature cure took place mediated by the Diels-Alder cycloaddition reaction. The reversible Diels-Alder RHM adhesive showed good thermal stability at the hotmelt application temperature. The green strength obtained after immediate cooling was highly tunable by choice of the prepolymers used in the formulation. The cure rate observed with the reversible RHM adhesive was similar to the moisture cure PUR benchmark and the new RHM adhesive showed versatile adhesion on a range of substrates. Mechanical and tensile properties were tunable depending on the choice of backbone present on the prepolymers used. A strong correlation between crosslink density and creep performance was observed. Repeated bonding, de-bonding and re-bonding experiments demonstrated a similar level of performance over multiple cycles. The adhesive reversibility would enable recycling or repositioning of bonded components several times without significant deterioration in performance. Diels-Alder networks with lower crosslink density have also been developed, which could be adapted for hotmelt pressure sensitive adhesive applications. Several polyfunctional furans and maleimide prepolymers were synthesized in multi-Kg scale to demonstrate industrial scalability.

## **Acknowledgements**

The authors wish to thank Donald E. Herr for useful discussion.

## **Conflict of interest**

The authors declare no conflicts of interest.

## **Author details**

Laxmisha M. Sridhar1 \*, Andrew T. Slark<sup>2</sup> and James A. Wilson2

1 Henkel Corporation, Rocky Hill, CT, USA

2 Department of Chemistry, University of Sheffield, Brook Hill, Sheffield, UK

\*Address all correspondence to<EMAIL_ADDRESS>
© 2021 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

*Furan Functionalized Polyesters and Polyurethanes for Thermally Reversible Reactive Hotmelt… DOI: http://dx.doi.org/10.5772/intechopen.100426*

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## **Chapter 5**


**Biodiversity Restoration and Renewable Energy from Hydropower: Conflict or Synergy?** Biodiversity Restoration and Renewable Energy from Hydropower: Conflict or Synergy?

DOI: 10.5772/intechopen.69134

Wondmagegn Tafesse Tirkaso, Ing‐Marie Gren, Leonard Sandin, Joel Segersten, David Spjut and Erik Degerman Wondmagegn Tafesse Tirkaso, Ing-Marie Gren, Leonard Sandin, Joel Segersten, David

Additional information is available at the end of the chapter Spjut and Erik Degerman

http://dx.doi.org/10.5772/intechopen.69134 Additional information is available at the end of the chapter

#### Abstract

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[46] Jelassi R. Eco-éthologie des peuplements d'Amphipodes au niveau des zones humides de la Tunisie [Thèse de doctorat en Biologie]. Faculté des Sciences de Tunis, Université

[47] Bouslama MF, El Gtari M, Charfi-Cheikhrouha F. Impact of environmental factors on zonation, abundance, and other biological parameters of two Tunisian populations of

[48] Fallaci M, Colombini I, Lagar M, Scapini F, Chelazzi L. Distribution patterns of different age classes and sexes in a Tyrrhenian population of *Talitrus saltator* (Montagu). Marine

[49] Colombini I, Aloia A, Bouslama MF, El Gtari M, Fallaci M, Ronconi L, Scapini F, Chelazzi L. Small-scale spatial and seasonal differences in the distribution of beach arthropods on the northern Tunisian coasts. Are species evenly distributed along the shore? Marine

[50] Williams JA. Burrow-zone distribution of the supralittoral Amphipod *Talitrus saltator* on Derbyhaven beach, Isle of Man-a possible mechanism for regulating desiccation stress?

*Talitrus saltator* (Amphipoda, Talitridae). Crustaceana. 2009;**82**(2):141-157

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de Tunis El Manar; 2014. p. 328

Biology. 2003;**142**:101-110

Biology, Berlin. 2002;**140**:1001-1012

Journal of Crustacean Biology. 1995;**15**:466-475

Hydropower plants have a negative impact on biodiversity by transforming stream habitat and hydrology and thereby affecting aquatic organisms negatively. The negative effects can be mitigated by releasing water into the old river bed. This study investigates if the measure of releasing water creates costs and if ecological conditions at the old river bed contribute to such an impact. To this end, we used the cost-minimization framework in economics for deriving hypotheses. Tests were made with data from a survey to 76 hydropower plants in Sweden with questions on existence of a cost, size of the plant, type of water release from reservoirs, characteristics of the dried downstream old river bed, and official statistics on ecological status of the downstream dried segments. The results showed that 42% of the plants reported no cost, measured as impact on electricity production, from release of water into downstream old river bed. We applied logit and probit models to explain the probability of a cost. Significant results were obtained were the electricity produced and program for minimum water discharges increase the probability of loss in electricity production, but favorable ecological conditions in the old river bed decrease the probability of a cost.

Keywords: hydropower, biodiversity, streams and rivers, restoration, old river bed, cost, survey data, econometrics, Sweden

#### 1. Introduction

Similar to many other countries, Sweden needs to comply with national and international targets on renewable energy and biodiversity provision. Hydropower is important for the

© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

© The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and eproduction in any medium, provided the original work is properly cited.

provision of renewable electricity production and accounts for approximately 47% of the total electricity production in the country [1]. Nuclear power is the second largest source of electricity and accounts for 34% of total energy production. Not only is hydropower a large source of electricity, but also acts a powerful regulatory device for the large fluctuations in demand and supply of electricity. Further, it is among the least expensive sources of energy as measured in SEK/kWh [2].

use inputs, such as labor and capital, at given prices to minimize costs for producing certain outputs. By applying the so-called duality theory a cost function can be derived which shows the relation between the output and production cost (e.g., [9]). The cost is then expressed as a function of given input prices, and output level. In our case, biodiversity improvement consti-

success of restoration, which can be measured as number of fish species or as a quality index, depends on ecological conditions at the site, Eil where l ¼ 1,.., m conditions such as length of the channel and natural water flow, and on restoration measures at the plant, Mig where g ¼ 1,.., h different restoration measures such as water discharges from the dam. The biodiversity

A crucial assumption in our analysis is that the plant manager minimizes total cost for

with a cost, Cig(Mig), and a maximum capacity of implementation, Mig. For example, there is a

large plant can have more expertise for implementing restoration measures than a small plant. On the other hand, a larger plant may give rise to more damages in the downstream waters, the mitigation of which requires costly restoration measures. The decision problem for the

,..,Mih; Ei1

¼ Qi (Mi1

maximum limit of water discharges into the channel. Plant size, Ki

g

ðMi1

CigðMig; Ki

, ::, Mih; Ei1

Þ

By applying the so-called duality theory to Eq. (1) we can express the cost of restoration at the

Our main interest is to investigate the impact on costs of a marginal increase in the restoration

measures need to be implemented. In this case, there is a conflict between biodiversity restoration and electricity provision since resources that could be used for electricity production are used for biodiversity restoration. On the other hand, a non-positive effect would imply the opposite interpretation. As shown in Eqs. (1) and (2), a test of this hypothesis requires data, not

.

Unfortunately, the necessary data presented in Section 2 is not available for a sufficient number of plants. Therefore, a survey was distributed to hydropower plants with dried channels. It

, …, Eim, Mi1

where i ¼ 1,.., n sites of the hydropower plants. The level of the output, or

Biodiversity Restoration and Renewable Energy from Hydropower: Conflict or Synergy?

, …, EimÞ ≥ Q�i and Mig ≤ Mig

, ::, Mih, Ki

. Each restoration measure is then associated

http://dx.doi.org/10.5772/intechopen.69134

, ecological conditions at the site, Eig, and

, increases since more of the restoration

Þ ð2Þ

, may also affect costs; a

ð1Þ

121

,.., Eim).

tutes the output Qi

at the site is then written as Qi

plant manager is then written as:

ambition, Q\*i

only on Ci

and Q\*i

3. Description of data

achieving a minimum level of biodiversity, Q\*i

MinCi ¼ X

Subject to Qi

plant as a function of the chosen restoration target Q\*i

, but also on Eil

the restoration measures, Mig, which is written as follows:

Ci ¼ Ci

. The hypothesis is that the cost, Ci

ðQ�i , Ei1

, Mig, and Ki

Mig

Establishments of hydropower plants change the hydrological conditions in the riverine landscape which affects habitats for animals and plants. Streams can be totally or partially dried and thereby destroying the habitats for several species and migration pathways for fish species. Although there is no national evidence on the extinction of species because of the hydropower production, the effects imply a degradation of habitats for red listed species [3], which goes against the national target of preserving biodiversity.

In order to mitigate these effects water power plants may be run with a release of water from the reservoir(s) into the downstream dry channel (the old natural river channel). However, this may only be achieved at a cost in terms of less electricity production and hence fulfillment of the target on renewable energy. This study investigates whether such a cost exists, and which factors contribute to the probability of its occurrence. To this end, we use the costminimization framework to derive testable hypotheses. Test are made with data from a survey on 76 hydropower plants in Sweden with questions on the existence of a cost in terms of negative impact on electricity production, the type of water release from reservoirs, and characteristics of the dried downstream channel and the plant. This data set was completed with official statistics on ecological status in the downstream segments. We use econometric methods to examine the impact of water discharges from the reservoir and other explanatory variables on electricity production. The dependent variable is a binary variable which equals 1 when electricity production is affected and 0 otherwise. We, therefore, use a probit model for the regression analysis, where we estimate how the explanatory variables affect the probability of losing electricity production.

There is a large body of literature on ecological effects of biodiversity restoration in freshwaters, such as wetland restoration (see reviews in Refs. [4, 5]). Despite this, the literature on the determination of costs of measures mitigating biodiversity degradation from hydropower plants is scant (e.g., [6–8]). The cost of restoration objects depends on the investment and management of the restoration measure as such, and on the ecological conditions at the site affecting the need and quality of restoration [5]. In our view, the main contribution of this study is the estimation of the explanatory power of ecological conditions and water release from reservoirs on the probability of a restoration cost in terms of reduction in electricity production.


*<IP_ADDRESS> Seed sterilisation*

Studying the effectiveness of various sterilisation methods (A, B, C, and D) for seed cultivation on solid media in tubes for callus formation (medium M&S + kinetin) and the cultivation of seeds on solid media in tubes to obtain sterile micro plants (medium M&S).

I.Using 0.8 grams of agar in the solid media (the amount of agar used for inoculation of cells was 0.8 grams).


**Abstract**

Neurotic disorders (NDs) are among the most common mental diseases leading to a decrease in the quality of life, lack of socialization, and increased mortality. The diagnosis and treatment of all types of NDs are challenging. In the light of the ongoing search for an effective and safe therapeutic strategy influencing certain aspects of ND pathogenesis, technologically processed highly diluted antibodies to S100 protein (TP Abs to S100) seem to be a promising treatment option for patients with NDs. TP Abs to S100 possess stress-protective, anxiolytic, antidepressant, antiamnestic, and neuroprotective activities. In the current review, we describe the mechanisms of action and pharmacological effects of TP Abs to S100 demonstrated in nonclinical (preclinical) and clinical studies. Based on the data, we tried to evaluate the future prospects of the TP Abs to S100 as the drug of choice for ND treatment.

**Keywords:** neurotic disorder, anxiety, anxiolytic therapy, S100 protein, somatoform disorder


**3.3 Concept for the didactical structural template for the PAGEL project**

To be able to use the QBLM and DST software infrastructure inside an actual course at FUH for the PAGEL project, first of all, a DST has to be conceptionally created. Therefore, the course and game flow described in [10] will be used as a basis.

Currently, the course "Industrial and Organizational Psychology" consists of three study books, which give the learners an overview of the theoretical background of industrial and organizational psychology. In addition, an AG should be developed to provide the learners with hands-on experience and action knowledge in the subdomain work task design, as described previously and in [10]. In the AG, the learners should experience the psychological effects of work task design for themselves. To check the learned factual and action CQs afterward, it should be possible that the game results are explained and analyzed using the previously acquired theoretical knowledge. In the end, the learners should receive a detailed overview of their results, including a review [10].

AS described previously, a DST has a hierarchical structure with different hierarchy types. At the top level of the hierarchy for a DST is the DST name. In the given case, this should be the name of the project PAGEL for easier identification. On the

level below is the play level. A play element represents a learning process. When one play element is finished, the next one starts. In the PAGEL project, three learning processes could be identified. These would be the preparation, the play, and the course completion. Finally, each play element has the respective act elements on the level below. An act describes activities or activity structures that can run parallel in a play. An activity element is a core element of the learning design. Activity structure elements can be used to combine several activities.

For the PAGEL project and the identified play elements, the structure of the DST results is shown below.

The preparation includes only the theoretical background. This was thought of as an act element because this element and its activities must be completed before the play and evaluation can take place. The activities here are the three study booklets, which the learners can work on in any order.

The play element contains the "work task simulation." In the PLC, it should be possible for the player to carry out various activities in parallel with so-called tools [10]. The tools are each represented as a separate activity.

After the play element preparation and game are completed, the play element course completion can start. The course completion is divided into three ACTs: final quiz, evaluation, and results, each of which has its own activity (**Figure 3**).